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Atomically Precise Nanochemistry
Atomically Precise Nanochemistry
Edited by
Rongchao Jin
Carnegie Mellon University
USA
De-en Jiang
Vanderbilt University
USA
This edition first published 2023
© 2023 John Wiley & Sons Ltd
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Library of Congress Cataloging-in-Publication Data

Names: Jin, Rongchao, editor. | Jiang, De-en, 1975– editor.
Title: Atomically precise nanochemistry / edited by Rongchao Jin and De-en
Jiang.
Description: Hoboken, NJ : Wiley, 2023. | Includes bibliographical
references and index.
Identifiers: LCCN 2022051975 (print) | LCCN 2022051976 (ebook) | ISBN
9781119788645 (cloth) | ISBN 9781119788683 (adobe pdf) | ISBN
9781119788652 (epub)
Subjects: LCSH: Nanochemistry.
Classification: LCC QC176.8.N35 A88 2023 (print) | LCC QC176.8.N35
(ebook) | DDC 620/.5–dc23/eng20230119
LC record available at https://lccn.loc.gov/2022051975
LC ebook record available at https://lccn.loc.gov/2022051976
Cover Design: Wiley
Cover Image: Courtesy of Dr. Yingwei Li.
Set in 9.5/12.5pt STIXTwoText by Straive, Pondicherry, India

v
Contents
List of Contributors xiii

Preface xvii
1 Introduction to Atomically Precise Nanochemistry 1

Rongchao Jin
1.1 Why Atomically Precise Nanochemistry? 1
1.1.1 Motivations from Nanoscience Research 1
1.1.2 Motivations from Inorganic Chemistry Research 5
1.1.3 Motivations from Gas Phase Cluster Research 6
1.1.4 Motivations from Other Areas 6
1.2 Types of Nanoclusters Covered in This Book 7
1.2.1 Atomically Precise Metal Nanoclusters (Au, Ag, Cu, Ni, Rh) 8
1.2.2 Endohedral Fullerenes and Graphene Nanoribbons 10
1.2.3 Zintl Clusters 10
1.2.4 Metal- Oxo Nanoclusters 11
1.3 Some Fundamental Aspects 12
1.3.1 Synthesis and Crystallization 12
1.3.2 Structural and Bonding Patterns 16
1.3.3 Transition from Nonmetallic to Metallic State: Emergence of Plasmon 25
1.3.4 Transition from Metal Complexes to the Cluster State: Emergence of Core 29
1.3.5 Doping and Alloying 32
1.3.6 Redox and Magnetism 33
1.3.7 Energy Gap Engineering 39
1.3.8 Assembly of Atomically Precise Nanoclusters 40
1.4 Some Applications 42
1.4.1 Chemical and Biological Sensing 43
1.4.2 Biomedical Imaging, Drug Delivery, and Therapy 44
1.4.3 Antibacteria 45
1.4.4 Solar Energy Conversion 45
1.4.5 Catalysis 45
1.5 Concluding Remarks 49
Acknowledgment 49
References 49
vi Contents
2 Total Synthesis of Thiolate-Protected Noble Metal Nanoclusters 57

Qiaofeng Yao, Yitao Cao, Tiankai Chen, and Jianping Xie
2.1 Introduction 57
2.2 Size Engineering of Metal Nanoclusters 58
2.2.1 Size Engineering by Reduction- Growth Strategy 58
2.2.2 Size Engineering by Size Conversion Strategy 62
2.3 Composition Engineering of Metal Nanoclusters 64
2.3.1 Metal Composition Engineering 64
2.3.2 Ligand Composition Engineering 70
2.4 Structure Engineering of Metal Nanoclusters 73
2.4.1 Pseudo-Isomerization 75
2.4.2 Isomerization 75
2.5 Top-Down Etching Reaction of Metal Nanoclusters 78
2.6 Conclusion and Outlooks 80
Contributions 83
References 83
3 Thiolated Gold Nanoclusters with Well-Defined Compositions and Structures 87

Wanmiao Gu and Zhikun Wu
3.1 Introduction 87
3.2 Synthesis, Purification, and Characterization of Gold Nanoclusters 88
3.2.1 Synthesis 88
3.2.1.1 Synthesis Strategy 89
3.2.1.2 Gold Salt (Complex) Reduction Method 89
3.2.1.3 Ligand Induction Method 91
3.2.1.4 Anti-Galvanic Reaction Method 91
3.2.2 Isolation and Purification 92
3.2.3 Characterization 94
3.3 Structures of Gold Nanoclusters 95
3.3.1 Kernel Structures of Aun(SR)m 96
3.3.2 Kernels Based on Tetrahedral Au4 Units 96
3.3.2.1 Kernels in fcc Structure 99
3.3.2.2 Kernels Arranged in hcp and bcc Fashions 99
3.3.2.3 Kernels in Mirror Symmetry and Dual-Packing (fcc and non-fcc) 101
3.3.2.4 Kernels Based on Icosahedral Au13 Unit 102
3.3.2.5 Kernels with Multiple Shells 105
3.3.3 Protecting Surface Motifs of Aun(SR)m Clusters 111
3.3.3.1 Staple-like Aux(SR)x+1 (x = 1, 2, 3, 4, 8) motifs 111
3.3.3.2 Ring-like Aux(SR)x (x = 4, 5, 6, 8) Motifs 111
3.3.3.3 Giant Au20S3(SR)18 and Au23S4(SR)18 Staple Motifs 112
3.3.3.4 Homo-Kernel Hetero-Staples 112
3.4 Properties and Applications 115
3.4.1 Properties 115
3.4.1.1 Optical Absorption 116
3.4.1.2 Photoluminescence 119
3.4.1.3 Chirality 123
3.4.1.4 Magnetism 124
3.4.2 Applications 125
3.4.2.1 Sensing 125
Contents vii
3.4.2.2 Biological Labeling and Biomedicine 127

3.4.2.3 Catalysis 127
3.5 Conclusion and Future Perspectives 130
Acknowledgments 131
References 131
4 Structural Design of Thiolate-Protected Gold Nanoclusters 141

Pengye Liu, Wenhua Han, and Wen Wu Xu
4.1 Introduction 141
4.2 Structural Design Based on “Divide and Protect” Rule 142
4.2.1 A Brief Introduction of the Idea 142
4.2.2 Atomic Structure of Au68(SH)32 142
4.2.3 Atomic Structure of Au68(SH)34 142
4.3 Structural Design via Redistributing the “Staple” Motifs on the Known Au Core
Structures 144
4.3.2 Atomic Structure of Au22(SH)17− 145
4.3.3 Atomic Structures of Au27(SH)20−, Au32(SR)21−, Au34(SR)23−, and Au36(SR)25− 146
4.4 Structural Design via Structural Evolution 149
4.4.2 Atomic Structures of Au60(SR)36, Au68(SR)40, and Au76(SR)44 150
4.4.3 Atomic Structure of Au58(SR)30 152
4.5 Structural Design via Grand Unified Model 153
4.5.2 Atomic Structures of Hollow Au36(SR)12 and Au42(SR)14 154
4.5.3 Atomic Structures of Au28(SR)20 155
4.6 Conclusion and Perspectives 155
Acknowledgment 156
References 156
5 Electrocatalysis on Atomically Precise Metal Nanoclusters 161

Hoeun Seong, Woojun Choi, Yongsung Jo, and Dongil Lee
5.1.1 Materials Design Strategy for Electrocatalysis 161
5.1.2 Atomically Precise Metal Nanoclusters as Electrocatalysts 163
5.2 Electrochemistry of Atomically Precise Metal Nanoclusters 164
5.2.1 Size-Dependent Voltammetry 164
5.2.2 Metal-Doped Gold Nanoclusters 166
5.2.3 Metal-Doped Silver Nanoclusters 169
5.3 Electrocatalytic Water Splitting on Atomically Precise Metal Nanoclusters 170
5.3.1 Hydrogen Evolution Reaction: Core Engineering 170
5.3.2 Hydrogen Evolution Reaction: Shell Engineering 172
5.3.3 Hydrogen Evolution Reaction on Ag Nanoclusters 173
5.3.4 Oxygen Evolution Reaction 176
5.4 Electrocatalytic Conversion of CO2 on Atomically Precise Metal Nanoclusters 178
5.4.1 Mechanistic Investigation of CO2RR on Au Nanoclusters 179
5.4.2 Identification of CO2RR Active Sites 181
5.4.3 CO2RR on Cu Nanoclusters 183
5.4.4 Syngas Production on Formulated Metal Nanoclusters 185
viii Contents
5.5 Conclusions and Outlook 187

Acknowledgments 188
References 188
6 Atomically Precise Metal Nanoclusters as Electrocatalysts: From Experiment

to Computational Insights 195
Fang Sun, Qing Tang, and De-en Jiang
6.2 Factors Affecting the Activity and Selectivity of NCs Electrocatalysis 196
6.2.1 Size Effect 196
6.2.2 Shape Effect 198
6.2.3 Ligands Effect 199
6.2.3.1 Different –R Groups in Thiolate Ligands 199
6.2.3.2 Different Types of Ligands 199
6.2.3.3 Ligand-on and -off Effect 200
6.2.4 Charge State Effect 201
6.2.5 Doping and Alloying Effect 202
6.3 Important Electrocatalytic Applications 205
6.3.1 Electrocatalytic Water Splitting 205
6.3.1.1 Water Electrolysis Process 205
6.3.1.2 Cathodic Water Reduction–HER 206
6.3.1.3 Anodic Water Oxidation–OER 208
6.3.2 Oxygen Reduction Reaction (ORR) 210
6.3.3 Electrochemical CO2 Reduction Reaction (CO2RR) 213
Acknowledgments 220
References 220
7 Ag Nanoclusters: Synthesis, Structure, and Properties 227

Manman Zhou and Manzhou Zhu
7.2 Synthetic Methods 228
7.2.1 One-Pot Synthesis 228
7.2.2 Ligand Exchange 228
7.2.3 Chemical Etching 229
7.2.4 Seeded Growth Method 229
7.3 Structure of Ag NCs 229
7.3.1 Based on Icosahedral Units’ Assembly 231
7.3.2 Based on Ag14 Units’ Assembly 235
7.3.3 Other Special Ag NCs 241
7.4 Properties of Ag NCs 245
7.4.1 Chirality of Ag NCs 245
7.4.2 Photoluminescence of Ag NCs 247
7.4.3 Catalytic Properties of Ag NCs 250
Acknowledgment 251
References 251
Contents ix
8 Atomically Precise Copper Nanoclusters: Syntheses, Structures, and Properties 257

Chunwei Dong, Saidkhodzha Nematulloev, Peng Yuan, and Osman M. Bakr
8.2 Syntheses of Copper NCs 258
8.2.1 Direct Synthesis 258
8.2.2 Indirect Synthesis: Nanocluster-to-Nanocluster Transformation 260
8.3 Structures of Copper NCs 261
8.3.1 Superatom-like Copper NCs without Hydrides 261
8.3.2 Superatom-like Copper NCs with Hydrides 263
8.3.3 Copper(I) Hydride NCs 265
8.3.3.1 Determination of Hydrides 265
8.3.3.2 Copper(I) Hydride NCs Determined by Single-Crystal Neutron Diffraction 265
8.3.3.3 Copper(I) Hydride NCs Determined by Single-Crystal X-ray Diffraction 268
8.4 Properties 270
8.4.1 Photoluminescence of Copper NCs 270
8.4.1.1 Aggregation-Induced Emission 271
8.4.1.2 Circularly Polarized Luminescence (CPL) 273
8.4.2 Catalytic Properties of Copper NCs 273
8.4.2.1 Reduction of CO2 273
8.4.2.2 “Click” Reaction 276
8.4.2.3 Hydrogenation 276
8.4.2.4 Carbonylation Reactions 276
8.4.3 Other Properties 276
8.4.3.1 Hydrogen Storage 276
8.4.3.2 Electronic Devices 277
8.5 Summary Comparison with Gold and Silver NCs 277
References 279
9 Atomically Precise Nanoclusters of Iron, Cobalt, and Nickel: Why Are They
So Rare? 285
Trevor W. Hayton
9.2 General Considerations 287
9.3 Synthesis of Ni APNCs 288
9.4 Synthesis of Co APNCs 294
9.5 Attempted Synthesis of Fe APNCs 297
Acknowledgments 300
References 300
10 Atomically Precise Heterometallic Rhodium Nanoclusters Stabilized by Carbonyl

Ligands 309
Guido Bussoli, Cristiana Cesari, Cristina Femoni, Maria C. Iapalucci,
Silvia Ruggieri, and Stefano Zacchini
10.1.1 Metal Carbonyl Clusters: A Brief Historical Overview 309
10.1.2 State of the Art on Rhodium Carbonyl Clusters 310
x Contents
10.2 Synthesis of Heterometallic Rhodium Carbonyl Nanoclusters 311

10.2.1 Synthesis of the [Rh12E(CO)27]n− Family of Nanoclusters 311
10.2.2 Growth of Rhodium Heterometallic Nanoclusters 314
10.2.2.1 Rh─Ge Nanoclusters 314
10.2.2.2 Rh─Sn Nanoclusters 316
10.2.2.3 Rh─Sb Nanoclusters 316
10.2.2.4 Rh─Bi Nanoclusters 319
10.3 Electron-Reservoir Behavior of Heterometallic Rhodium Nanoclusters 319
10.4 Conclusions and Perspectives 322
Acknowledgments 324
References 324
11 Endohedral Fullerenes: Atomically Precise Doping Inside Nano Carbon Cages 331
Yang-Rong Yao, Jiawei Qiu, Lihao Zheng, Hongjie Jiang, Yunpeng Xia, and Ning Chen
11.2 Synthesis of Endohedral Metallofullerenes 332
11.3 Fullerene Structures Tuned by Endohedral Doping 334
11.3.1 Geometry of Empty and Endohedral Fullerene Cage Structures 334
11.3.2 Conventional Endohedral Metallofullerenes 336
11.3.2.1 Mono-Metallofullerens 336
11.3.2.2 Di-Metallofullerenes 337
11.3.3 Clusterfullerenes 339
11.3.3.1 Nitride Clusterfullerenes 339
11.3.3.2 Carbide Clusterfullerenes 339
11.3.3.3 Oxide and Sulfide Clusterfullerenes 341
11.3.3.4 Carbonitride and Cyanide Clusterfullerenes 341
11.4 Properties Tuned by Endohedral Doping 342
11.4.1 Spectroscopic Properties 342
11.4.1.1 NMR Spectroscopy 343
11.4.1.2 Absorption Spectroscopy 344
11.4.1.3 Vibrational Spectroscopy 347
11.4.2 Electrochemical Properties 349
11.4.2.1 Conventional Endohedral Metallofullerenes 349
11.4.2.2 Clusterfullerenes 351
11.4.3 Magnetic Properties 353
11.4.3.1 Dimetallofullerenes 353
11.4.3.2 Clusterfullerenes 354
11.5 Chemical Reactivity Tune by Endohedral Doping 358
11.5.1 Impact of Endohedral Doping on the Reactivity of Fullerene Cages 358
11.5.2 Chemical Reactivity of Endohedral Fullerenes Altered by Atomically Endohedral
Doping 360
11.6 Conclusions and Perspectives 362
References 362
12 On-Surface Synthesis of Polyacenes and Narrow Band-Gap Graphene Nanoribbons 373

Hironobu Hayashi and Hiroko Yamada
12.1.1 Nanocarbon Materials 374
12.1.2 Graphene Nanoribbons 374
Contents xi
12.2 Bottom-Up Synthesis of Graphene Nanoribbons 375

12.3 On-Surface Synthesis of Narrow Bandgap Armchair-Type Graphene Nanoribbons 378
12.4 On-Surface Synthesis of Polyacenes as Partial Structure of Zigzag-Type Graphene
Nanoribbons 382
Acknowledgments 390
References 390
13 A Branch of Zintl Chemistry: Metal Clusters of Group 15 Elements 395

Yu-He Xus, Nioolay V. Toachenoos, Aliaro Muñoi-Castros, Alexannder I. olndyreis, annd
Zhong-Ming Sun
13.1.1 Homoatomic Group 15 Clusters 395
13.1.2 Bonding Concepts 396
13.1.3 Aromaticity in Zintl Chemistry 397
13.2 Complex Coordination Modes in Arsenic Clusters 399
13.3 Antimony Clusters with Aromaticity and Anti-Aromaticity 401
13.4 Recent Advances in Bismuth- Containing Compounds 408
13.5 Ternary Clusters Containing Group 15 Elements 411
References 415
14 Exploration of Controllable Synthesis and Structural Diversity of Titanium─Oxo

Clusters 423
Mei-Yan Gao, Lei Zhang, and Jian Zhang
14.2 Coordination Delayed Hydrolysis Strategy 425
14.2.1 Solvothermal Synthesis 426
14.2.2 Aqueous Sol- Gel Synthesis 426
14.2.3 Ionothermal Synthesis 427
14.2.4 Solid-State-Like Synthesis 427
14.3 Ti─O Core Diversity 427
14.3.1 Dense Structures 431
14.3.2 Wheel-Shaped Structures 431
14.3.3 Sphere-Shaped Structures 431
14.3.4 Multicluster Structures 432
14.4 Ligand Diversity 432
14.4.1 Carboxylate Ligands 433
14.4.2 Phosphonate Ligands 433
14.4.3 Polyphenolic Ligands 435
14.4.4 Sulfate Ligands 436
14.4.5 Nitrogen Heterocyclic Ligands 437
14.5 Metal-Doping Diversity 438
14.5.1 Transition Metal Doping 439
14.5.2 Rare Earth Metal Doping 440
14.6 Structural Influence on Properties and Applications 441
Acknowledgment 446
References 446
xii Contents
15 Atom-Precise Cluster-Assembled Materials: Requirement and Progresses 453

Sourav Biswas, Panpan Sun, Xia Xin, Sukhendu Mandal, and Di Sun
15.2 Prospect of Cluster-Assembling Process and Their Classification 454
15.2.1 Nanocluster Assembly in Crystal Lattice through Surface Ligand Interaction 455
15.2.2 Nanocluster Assembly through Metal–Metal Bonds 456
15.2.3 Nanocluster Assembly through Linkers 461
15.2.3.1 One-Dimensional Nanocluster Assembly 463
15.2.3.2 Two-Dimensional Nanocluster Assembly 465
15.2.3.3 Three-Dimensional Nanocluster Assembly 469
15.2.4 Nanocluster Assembly through Aggregation 470
Notes 474
Acknowledgments 475
References 475
16 Coinage Metal Cluster-Assembled Materials 479

Zhao-Yang Wang and Shuang-Quan Zang
16.2 Structures of Metal Cluster-Assembled Materials 480
16.2.1 Silver Cluster-Assembled Materials (SCAMs) 480
16.2.1.1 Simple Ion Linker 480
16.2.1.2 POMs Linker 482
16.2.1.3 Organic Linker 482
16.2.2 Gold Cluster-Assembled Materials (GCAMs) 491
16.2.3 Copper Cluster-Assembled Materials (CCAMs) 492
16.3 Applications 493
16.3.1 Ratiometric Luminescent Temperature Sensing 494
16.3.2 Luminescent Sensing and Identifying O2 and VOCs 495
16.3.3 Catalytic Properties 495
16.3.4 Anti-Superbacteria 498
16.4 Conclusion 499
Acknowledgments 499
References 499
Index 503
xiii
List of Contributors
Osman M. Bakr Ning Chen

KAUST Catalysis Center (KCC) College of Chemistry
Division of Physical Sciences and Engineering Chemical Engineering
King Abdullah University of Science and Materials Science
and Technology (KAUST) and State Key Laboratory of Radiation Medicine
Dhuwal, Saudi Arabia and Protection
Soochow University, Suzhou, Jiangsu, China
Sourav Biswas
School of Chemistry
Indian Institute of Science Education Tiankai Chen
and Research Thiruvananthapuram Department of Chemical and Biomolecular
Kerala, India Engineering
National University of Singapore
Alexander I. Boldyrev Singapore
Department of Chemistry and Biochemistry
Utah State University
Woojun Choi
Logan, USA
Department of Chemistry and Medical Chemistry
Yonsei University
Guido Bussoli
Wonju, Gangwon, Republic of Korea
Department of Industrial Chemistry
“Toso Montanari”
University of Bologna Chunwei Dong
Bologna, Italy KAUST Catalysis Center (KCC)
Division of Physical Sciences
Yitao Cao and Engineering
Department of Chemical and Biomolecular King Abdullah University of Science
Engineering and Technology (KAUST)
National University of Singapore Thuwal, Saudi Arabia
Singapore
Cristiana Cesari Cristina Femoni

Department of Industrial Chemistry Department of Industrial Chemistry
“Toso Montanari” “Toso Montanari”
University of Bologna University of Bologna
Bologna, Italy Bologna, Italy
xiv List oA Contriiutors
Mei-Yan Gao Rongchao Jin

State Key Laboratory of Structural Chemistry Department of Chemistry
Fujian Institute of Research on the Carnegie Mellon University
Structure of Matter Pittsburgh, USA
Chinese Academy of Sciences
China Yongsung Jo
and Department of Chemistry
Yonsei University
Department of Chemical Sciences Seoul, Republic of Korea
Bernal Institute, University of Limerick
Limerick, Limerick County
Dongil Lee
Republic of Ireland
Department of Chemistry
Wanmiao Gu Yonsei University
Key Laboratory of Materials Physics Seoul, Republic of Korea
Anhui Key Laboratory of Nanomaterials
and Nanotechnology Pengye Liu
CAS Center for Excellence in Nanoscience Department of Physics, School of Physical
Institute of Solid State Physics Science and Technology
Chinese Academy of Sciences Ningbo University
Hefei, China Ningbo, China
Wenhua Han Sukhendu Mandal

Department of Physics, School of Physical School of Chemistry
Science and Technology Indian Institute of Science Education
Ningbo University and Research Thiruvananthapuram
Ningbo, China Kerala, India
Hironobu Hayashi
Division of Materials Science Alvaro Muñoz-Castro
Nara Institute of Science and Technology Grupo de Química Inorgánica y Materiales
Japan Moleculares
Facultad de Ingeniería
Trevor W. Hayton Universidad Autonoma de Chile
Department of Chemistry and Biochemistry El Llano Subercaseaux, Santiago, Chile
University of California Santa Barbara
Santa Barbara, USA Saidkhodzha Nematulloev
KAUST Catalysis Center (KCC)
Maria C. Iapalucci
Division of Physical Sciences and Engineering
Department of Industrial Chemistry
King Abdullah University of Science
“Toso Montanari”
and Technology (KAUST)
University of Bologna
Thuwal, Saudi Arabia
Bologna, Italy
De-en Jiang Jiawei Qiu

Department of Chemical and Biomolecular College of Chemistry
Engineering Chemical Engineering and Materials Science
Vanderbilt University and State Key Laboratory of Radiation Medicine
Nashville, USA and Protection
Hongjie Jiang
College of Chemistry Silvia Ruggieri
Chemical Engineering and Materials Science Laboratory of Luminescent Materials
and State Key Laboratory of Radiation Medicine Department of Biotechnology
and Protection University of Verona
Soochow University, Suzhou, Jiangsu, China Verona, Italy
List oA Contriiutors xv
Hoeun Seong Xin Xia

Department of Chemistry School of Chemistry and Chemical Engineering
Yonsei University State Key Laboratory of Crystal Materials
Seoul, Republic of Korea Shandong University, Ji’nan, China
Di Sun
Yunpeng Xia
School of Chemistry and Chemical Engineering
College of Chemistry
State Key Laboratory of Crystal Materials
Chemical Engineering and Materials Science
Shandong University, Ji’nan, China
and State Key Laboratory of Radiation Medicine
and Protection
Fang Sun
Chongqing Key Laboratory of Theoretical
and Computational Chemistry Jianping Xie
Chongqing University, Chongqing, China Joint School of National University of Singapore
and Tianjin University
Panpan Sun International Campus of Tianjin University
School of Chemistry and Chemical Engineering Fujian, China
State Key Laboratory of Crystal Materials
and
Shandong University, Ji’nan, China
Department of Chemical and Biomolecular
Zhong-Ming Sun Engineering
State Key Laboratory of Elemento- Organic National University of Singapore
Chemistry School of Materials Science Singapore
and Engineering Nankai University
Tianjin, China
Wen Wu Xu
Department of Physics, School of Physical
Qing Tang
Science and Technology
Ningbo University
Chongqing Key Laboratory of Theoretical
Ningbo, China
and Computational Chemistry
Chongqing University, Chongqing, China
Yu-He Xu
Nikolay V. Tkachenko State Key Laboratory of Elemento- Organic
Department of Chemistry and Biochemistry Chemistry
Utah State University School of Materials Science and Engineering
Logan, USA Nankai University, China
Zhao-Yang Wang
Hiroko Yamada
Henan Key Laboratory of Crystalline Molecular
Division of Materials Science
Functional Materials
Nara Institute of Science and Technology
Henan International Joint Laboratory of Tumor
Japan
Theranostical Cluster Materials
Green Catalysis Center
and College of Chemistry Qiaofeng Yao
Zhengzhou University, Zhengzhou, China Joint School of National University of Singapore
and Tianjin University
Zhikun Wu International Campus of Tianjin University
Key Laboratory of Materials Physics Fujian, China
Anhui Key Laboratory of Nanomaterials
and
and Nanotechnology
CAS Center for Excellence in Nanoscience Department of Chemical and Biomolecular
Institute of Solid State Physics Engineering
Chinese Academy of Sciences National University of Singapore
Hefei, China Singapore
xvi List oA Contriiutors
Yang-Rong Yao Lei Zhang

College of Chemistry State Key Laboratory of Structural Chemistry
Chemical Engineering and Materials Science Fujian Institute of Research on the
and State Key Laboratory of Radiation Medicine Structure of Matter
and Protection Chinese Academy of Sciences
Soochow University, Suzhou, Jiangsu, China Fujian, China
and and
Department of Materials Science and Institute of Modern Optics
Engineering College of Electronic Information and
University of Science and Technology of China Optical Engineering
Hefei, China Nankai University, Tianjin, China
Peng Yuan Lihao Zheng

KAUST Catalysis Center (KCC) College of Chemistry
Division of Physical Sciences and Engineering Chemical Engineering and Materials Science
King Abdullah University of Science and and State Key Laboratory of Radiation Medicine
Technology (KAUST) and Protection
Thuwal, Saudi Arabia Soochow University, Suzhou, Jiangsu, China
Stefano Zacchini Manman Zhou

Department of Industrial Chemistry Department of Chemistry and Centre for Atomic
“Toso Montanari” Engineering of Advanced Materials
University of Bologna Key Laboratory of Structure and Functional
Bologna, Italy Regulation of Hybrid Materials of Ministry
of Education
Shuang-Quan Zang Anhui Province Key Laboratory of Chemistry
Henan Key Laboratory of Crystalline Molecular for Inorganic/Organic Hybrid Functionalized
Functional Materials Materials
Henan International Joint Laboratory of Tumor Anhui University, Anhui, China
Theranostical Cluster Materials
Green Catalysis Center Manzhou Zhu
and College of Chemistry Department of Chemistry and Centre for Atomic
Zhengzhou University, Zhengzhou China Engineering of Advanced Materials
Key Laboratory of Structure and Functional
Jian Zhang Regulation of Hybrid Materials of Ministry
State Key Laboratory of Structural Chemistry of Education
Fujian Institute of Research on the Anhui Province Key Laboratory of Chemistry
Structure of Matter for Inorganic/Organic Hybrid Functionalized
Chinese Academy of Sciences Materials
Fujian, China Anhui University, Anhui, China
xvii
Preface
Chemists have long been motivated to create atomically precise nanoclusters, not only for
addressing some fundamental issues that were not possible to tackle with imprecise nanoparti-
cles but also to provide new opportunities for applications such as catalysis, optics, and biomedi-
cine. Given the breadth of the book, De-en and I decided to invite a number of experts who are
working on various types of atomically precise nanoclusters. We thank all the experts for their
warm support of the book and timely completion of the chapters. Due to space limitations, we
must apologize to some colleagues for missing their excellent work that could not be included in
this book.
This book comprises 16 chapters. Chapter 1 provides an introduction to atomically precise nano-
chemistry. Chapters 2 to 10 cover atomically precise metal nanoclusters, such as Au, Ag, Cu, Ni,
Rh, and the doped/alloyed nanoclusters, as well as the electrocatalytic application in CO2 reduc-
tion and water splitting. Endohedral metallofullerenes, graphene nanoribbons, Zintl clusters, and
Ti-oxo nanoclusters are discussed in Chapters 11 to 14, respectively. Finally, Chapters 15 and 16
are devoted to the assembly of nanoclusters (such as Au, Ag, and Cu), including the crystalline
assembly and the use of nanoclusters as nodes for constructing special types of metal-organic
frameworks, as well as the sensing and other applications. The atomic-level control in the synthe-
sis, the new types of structures, and the physical/chemical properties of nanoclusters are illus-
trated in various chapters. This book contains not only experimental contributions but also
theoretical insights into the atomic and electronic structures, as well as the catalytic mechanisms.
We expect this book to be suitable for graduate and undergraduate students, researchers, and
industry practitioners.
Overall, the concept of atomic precision is expected to have a major impact on future nanosci-
ence research and other areas. We hope that atomically precise nanochemistry will serve as a hub
for the unification of various research areas in which precision materials are being created and
studied. In future research, exquisite nanochemistry will surely bring exciting opportunities in
both fundamental research and practical applications. Progress in various types of atomically pre-
cise nanoclusters and the hybridization of two or more types of nanoclusters, as well as the assem-
bly of nanoclusters into meso- and macroscopic functional materials, will lead to more exciting
frontiers.
Rongchao Jin and De-en Jiang

October 2022
1
Introduction to Atomically Precise Nanochemistry

Rongchao Jin
Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA, 15213, USA
1.1 Why Atomically Precise Nanochemistry?
Since the beginning of the twenty-first century, nanoscience has made significant progress [1–8],
especially in the creation of a variety of nanostructures with size and shape control and the discov-
ery of new phenomena at the nanoscale. The rapid progress of nanoscience heavily relies on the
synthetic breakthroughs [1–7, 9]. In terms of chemical synthesis, Mother Nature is indeed the
master, evidenced by, for example, the creation of giant molecules such as DNA and proteins from
atomic building blocks, and even the buildup of complex photosynthesis machinery, all being at
the level of atomic precision. While there is still a long way to go for chemists to be on par with
Mother Nature, we expect that nanochemistry will make giant leaps in the near future toward
controlling nanostructures with atomic precision [10].
Beside the nanoscience field, the pursuit of atomic precision is also of critical importance in
other areas (Scheme 1.1), including inorganic cluster chemistry, gas phase cluster science and
solid-state materials science, as well as supramolecular chemistry. In moving toward larger sizes
and building up complex architectures (Figure 1.1), precise control over size and structure will
certainly become more challenging, yet highly exciting and rewarding [11].
1.1.1 Motivations from Nanoscience Research

Over the past two decades, significant advances have been made in controlling the size, shape,
crystallinity, and composition of many types of nanoparticles, including metal nanoparticles (e.g.
Au, Ag, Pt, Pd, Rh), semiconductor nanocrystals (e.g. CdSe, InP), and magnetic nanoparticles (e.g.
Fe, Co, Ni), all with high monodispersity (e.g. size distributions of 5–10%). In addition, several
shape-controlled nanostructures have been successfully developed, [1–9] such as the nanorods/
nanowires (1D) and nanoprisms (2D). Research on the anisotropic nanostructures (both 1D and
2D) has significantly expanded the fundamental understanding of the new physicochemical prop-
erties of nanostructures enabled by shape control. Based on the new properties observed, a wide
range of applications, such as sensing, catalysis, optics, and electronics, have been designed. New
frontiers keep emerging, which has greatly pushed the frontier of nanoscience research.
Despite the impressive progress in nanoscience, some issues still exist. Below we briefly discuss
a few issues that hamper nanoscience research from going deeper. By pursuing atomic precision,
Atomically Precise Nanochemistry, First Edition. Edited by Rongchao Jin and De-en Jiang.
© 2023 John Wiley & Sons Ltd. Published 2023 by John Wiley & Sons Ltd.
2 1 Intronduction to Atomically Precise Nanochemistry
Solid state
2D materials, edge control,
defects engineering
Gas phase Nanoscience

cluster science Size/shape control,
Metals, nonmetals, plasmon, exciton,
molecule-clusters
Atomically precise superparamagnetism
nanochemistry
1Å 1 nm 10 nm 100 nm
Inorganic chemistry Supramolecular

cluster research chemistry
Metals, metal-oxo, Metallo-organic,
Zintl chemistry Organic
Scheme 1.1 Atomically precise nanochemistry as a “hub” for nanoscience, inorganic cluster chemistry, gas
phase cluster science, and other areas.
nm
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0
Figure 1.1 Examples of giant structures of nanoclusters and molecular architectures determined by X-ray
crystallography. Source: Reprinted with permission from [11]. © 2021 American Chemical Society.
those issues can be overcome or at least alleviated, which will enable nanoscience research to
reach a new level.
First of all, the polydispersity of nanoparticles (NPs) has long been an issue in nanoscience
research. The synthesis of NPs tends to produce particles with a polydispersity (more or less).
When the polydispersity is controlled to be better than 15% (e.g. 10 ± 1.5 nm), such NPs are typi-
cally called monodisperse. Although highly monodisperse NPs (e.g. polydispersity down to 5%)
have also been made in some cases (Figure 1.2a/b), these NPs are still not of the same size at the
atomic scale. In other words, no two NPs are the same! Therefore, a major dream of nanochemists
has long been to synthesize truly uniform NPs (i.e. atomically precise NPs). This dream has now
1.1 hy Atomically Precise Nanochemistryy 3
(a) (b) 40
30
Population (%)
20
10
20 nm 0
4.6 4.8 5.0 5.2 5.4
Size (nm)
(c) (d)
7394 Au25(SC2H4Ph)18
Intensity
1 nm
3000 6000 9000 12000 15000 18000

Mass (m/z)
Figure 1.2 Comparison between regular nanoparticles and atomically precise nanoclusters. (a) Monodisperse
nanoparticles (average: ~5 nm, standard deviation: ~5%) imaged by transmission electron microscopy;
(b) Typical size distribution (e.g. 5 ± 0.3 nm diameter); (c) Atomically precise Au25(SC2H4Ph)18 nanoclusters
(1 nm metal core diameter, −C2H4Ph groups are omitted for clarity) assembled in a single crystal; (d) Mass
spectrometry characterization of Au25(SC2H4Ph)18. Source: Reprinted with permission from [12]. © 2014
Springer.
been partially realized in the case of ultrasmall gold NPs of 1–3 nm in size (Figure 1.2c/d) and sil-
ver as well [10]. Such atomically precise NPs are often termed as nanoclusters (NCs) in order to
differentiate them from the regular NPs. The success in obtaining atomically precise NCs is criti-
cally important, because they can serve as models for nanochemists to gain fundamental under-
standing of some important issues that were previously not feasible to tackle, such as the
nanoparticle isomerism, the origin of surface plasmon resonance (SPR), and chemical bonding
evolution with size [10].
Second, the surface of NPs often remains poorly controlled in the synthesis and thus poorly
understood. Questions on the precise composition of the surface adsorbates (i.e. stabilizers) and
how the stabilizers are adsorbed on the particle surface are generally not known for most nanopar-
ticle samples. While transmission electron microscopy (TEM) and various spectroscopy techniques
are powerful in characterizing NPs, they often cannot reveal the true composition and bonding
structure of the surface. For solution phase NPs, the surface includes the organic stabilizers and
the interface to the inorganic core. This organic–inorganic interface (Figure 1.3a) is unfortunately
very tough to study, [12, 13] because TEM is ineffective in imaging the particle surface (Figure 1.3b)
(a) (b) (c)
S
S
S
S
S
S
5 nm
Figure 1.3 Thiolate-protected gold nanoparticles. (a) Cartoon, (b) High resolution TEM image (ligands
invisible), (c) X-ray structure of atomically precise Au246(SPh-p-CH3)80 (metal core diameter: 2.2 nm) with
both metal atoms and surface ligands visible. Source: Adapted with permission from [10, 13]. © 2016
American Chemical Society and American Association for the Advancement of Science.
due to insufficient electron scattering by organics (e.g. light atoms of S, C, N, O, and H). While
scanning probe microscopy [14] can readily reveal the surface molecules via van der Waals forces
or tunneling currents, unfortunately it is incapable of showing the underlying interface between
the inorganic core and surface ligands. In molecular science, many spectroscopic tools have been
developed and are very powerful for analyzing molecules, such as nuclear magnetic resonance
(NMR), infrared (IR), and Raman scattering, but when they are used for NPs, the polydispersity
and heterogeneity of regular NPs make it very difficult (or unreliable) to correlate the NMR/IR/
Raman signals with imprecise NPs. Thus, well-defined NPs are critically needed for fundamental
research, especially in order to understand the surface composition and structure. By revealing the
interfacial bonding between the stabilizers and the underlying inorganic core through X-ray crys-
tallography (XRC) (Figure 1.3c), many fundamental questions could be addressed, such as the
nature of active sites in nanocatalysis, charge transfer and catalytic mechanisms, photolumines-
cence blinking, surface magnetism, self-assembled monolayer (SAM) structure, and nanoparticle
assembly mechanisms [10, 13].
Third, conventional NPs often possess various defects in the interior and/or on the surface,
which are highly detrimental to many physical and chemical properties, including the stability of
NPs, photoluminescence, and charge transport. How to eliminate those defects? Is it possible to
create perfect NPs? These questions are of paramount importance in nanoscience research. Thus,
new chemistry should be developed to attain atomically precise NPs. Even more exciting is to
develop capabilities of tailoring or engineering the NP surface for specific applications, e.g. cataly-
sis and biomedicine. These tasks call for the atomically precise NCs.
Fourth, the mechanisms for shape-controlled synthesis of nanoparticles are still not well under-
stood, such as the nucleation and growth mechanisms. For example, small nanoprisms (<10 nm)
were observed as nuclei in the photo- or plasmon-induced transformation of spherical Ag NPs to
nanoprisms, [1, 9] but thus far it is not yet clear how the transformation occurs during the nuclea-
tion stage [15, 16], nor how the nuclei subsequently grow to larger nanoprisms (e.g. atom by atom
in the classical mechanism, particle edge-to-edge fusion [9], or other unknown processes).
Considering the important roles of stabilizers, facet-selective binding of stabilizers (or ligands) is
often invoked to explain the formation of nonspherical (=anisotropic) nanostructures, but many
details are still unknown yet, including how the ligands are bonded to the surface atoms on specific
facets such as {111} and {100} of nanoparticles, and what the bonding geometry is (e.g. terminal vs.
bridging bonds). To understand the mechanism for shape control and relevant issues, atomic-level
1.1 hy Atomically Precise Nanochemistryy 5
information for both the nucleation and growth processes is critically needed, in which atomically
precise NCs may provide useful hints.
Last but not least, the applications of NPs such as nanocatalysis and nanomedicine require the
precise knowledge of the total structure of the NP, not just the core size/shape from TEM analysis.
In nanocatalysis, the adsorption of reactant(s) occurs on the surface; thus, without knowing the
surface composition and structure, it would not be possible to understand the catalytic mechanism
and provide the design principles for efficient catalysts [17]. The same is true in nanomedicine [8].
Upon the nanoparticles (e.g. carrying DNA or drug compounds) being injected into an animal or
human body, these nanoparticles first experience interactions with proteins in blood, glutathione
in cells, and other types of biomolecules. Knowing the surface of nanoparticles will be critically
important and can lead to a fundamental understanding of the biodistribution and pharmacoki-
netics [18, 19]; hence, precision medicine can be designed.
Beside the research efforts toward atomically precise metal NCs, it is worth noting that the pur-
suit of atomic precision in semiconductor quantum dot is also emerging [20–22]. In quantum dots,
the strong quantum confinement makes the properties extremely sensitive to size variation, thus,
precise control over quantum dot size and structural uniformity is very pressing. Efforts toward
such goals are underway [22, 23]. In the case of magnetic NPs, the surface disorder often results in
electron spin randomization (so-called spin canting), hence, a lower magnetization than the bulk
value, but in certain cases an enhanced magnetization was observed [24, 25]. To unravel the mys-
teries, a precise understanding of the surface atomic structure should be first obtained [26].
To address all the above important issues and many other fundamental ones in nanoscience,
atomically well-defined NPs are critically needed. Nanoscientists are thus strongly motivated to
develop atomically precise nanochemistry.
1.1.2 Motivations from Inorganic Chemistry Research

The cluster state is also of wide interest in the inorganic chemistry field. Understanding the chemi-
cal bonding pattern in the cluster state and the pattern evolution with increasing size has long been
a central task. Since the early twentieth century, research in inorganic chemistry has led to the
production of metal clusters (typically in ligand-protected form) and also boron clusters, Zintl clus-
ters, and metal-oxo nanoclusters. There is strong interest in pushing up the size of such clusters.
Boron cluster research was pioneered by Stock in the 1910s [27] and has significantly expanded
the concept of chemical bonding [28]. In contrast to classical covalent bonds in which two electrons
are shared by two atoms or centers (denoted “2c-2e,” so-called Lewis pair [29]), multicenter bonding
such as 3c-2e [30] was introduced for boron clusters. In addition, the concept of three-dimensional
(3D) aromaticity was also put forth [31, 32], which is in contrast with the 2D case, i.e. Hückel aro-
maticity. Such aromaticity rules have been widely applied in later research in different areas.
The Zintl cluster research was initiated by Zintl in the 1930s [33], such as As73− and Sb73− in
liquid ammonia. A striking feature is that Zintl clusters are bare (without the need of ligand pro-
tection in solution phase) [34]. Larger sizes are such as [As@Ni12@As20]3−, [35] [Au8Pb33]6−, and
[Au12Pb44]8− [36]. Understanding the electronic structure of Zintl clusters and the size evolution is
of particular interest [34, 37]. Several theories, such as the Zintl-Klemm concept [38], were devel-
oped in early work. The Wade-Mingos electron counting rules from the polyhedral borane clusters
were later introduced into the Zintl cluster field. The concepts of aromaticity and multicenter
delocalized bonding [32, 39], as well as the superatom electronic picture, [37d, 40] have all been
applied to Zintl clusters.
Another line of inorganic cluster chemistry involves the metal-oxo chemistry or polyoxometa-
late clusters (POM), which also features atomic precision [41]. The POMs are closely relevant to
the corresponding metal oxide in terms of composition and structure, [42] thus, atomically precise
POMs can serve as molecular or nanoscale models for metal oxides, such as Ti-oxo NCs for mod-
eling TiO2 and Ce-oxo for CeO2. Using the Ti-oxo cluster (TOC) system as an example, the inor-
ganic Ti─O core is coordinated by organic or inorganic ligands. In early work, a hydrolysis product
of titanium tetraethoxide was identified by XRC to be [Ti7O4(OEt)20] in 1967 [43]. Since then,
many TOCs have been reported, such as Ti42, Ti44, and Ti52 [44–46]. Their structures can be con-
trolled, such as spherical cages, rings or wheels, and many types of dense structures [41]. In addi-
tion to monometallic TOCs, there are also bimetallic ones with doped ions being main group ions,
transition metal ions, and lanthanide ions [41]. The incorporation of Ag clusters into TOCs is quite
appealing, such as the Ag14@Ti16-oxo nanocluster [47].
Finally, metal coordination-based supramolecular chemistry has also moved toward the
nanoscale by creating ever-larger nanostructures, such as wheels/rings, cages, and polyhedrons, as
well as tubular architectures [11]. The construction of large and exquisite molecular architectures
calls for new development of nanochemistry [48].
1.1.3 Motivations from Gas Phase Cluster Research

The field of gas phase cluster science has moved from small sizes (several to a dozen atoms in
earlier research) to larger sizes in the current efforts [49]. Since the 1960s, intense research on gas
phase clusters has been carried out, including inert-gas-element clusters (e.g. xenon clusters, Xen),
metal clusters (e.g. Nan clusters), carbon clusters (Cn), water clusters ([H2O]n), and many other
types [50]. The Xen cluster research led to an important insight into the structural stability of clus-
ters, i.e. the formation of icosahedral packing structures, such as the one-shelled Xe13, two-shelled
Xe55, and three-shelled Xe147 [51]. These are called the geometric magic numbers, and the atomic
shell closing endows high stability to the clusters.
In the 1980s, research on gas phase Nan clusters led to another important concept, that is, the elec-
tron shell closing of 1S 1P 2S 1D . . . , with notable sizes of Na8, Na34, Na58, and Na92 (so-called super-
atoms because of the atomic-like orbitals in such clusters) [52]. Much work has also been done on gas
phase gold clusters, [53, 54] and theoretical computations on the 2D to 3D structure transition
(Figure 1.4) [55, 56]. To investigate the evolution of the superatom electronic shell picture, larger
sized NCs should be pursued. As the size boundary moves up, the cluster science indeed merges with
nanoscience. Preparation of clusters in gas phase with hundreds of atoms per core has been pursued
in recent years, [49] although major effort is still required in the pursuit of atomic precision.
Carbon clusters (or fullerenes) are one of the significant areas in gas phase cluster research [57,
58]. Fullerenes are typically produced using the electric arc discharge or thermal chemical vapor
deposition (CVD) method. From the initial discovery of C60 in 1985, a variety of sizes have been
reported, with smaller ones such as C20, C24, C28, C32, C36 and larger ones such as C70, C80, C82, C108
and even up to C540 [59]. The size-dependent structure, electronic, and optical properties of Cn are
under active investigation, and the cage structure of Cn clusters is particularly appealing for encap-
sulating atoms, molecules, and clusters of few-atom in size, forming endohedral clusters [60]. New
additions to the nanocarbon family also include the atomically precise graphene nanoribbons
(GNR) [61] and some other forms.
1.1.4 Motivations from Other Areas

The concept of atomic precision is also critically important in solid-state materials. A variety of
solid-state materials are being intensively pursued in the field of materials science, such as the low
dimensional materials (2D van der Waals materials, stacked 2D materials, etc.) and quantum
1.2 Types oA Nanoclusters Coierend in This ooo 7
Au+4 Au+5 Au+6 Au+7 Au+8
Au+9 Au+10 Au+11 Au+12 Au+13
Au+14 +
Au15 Au+16
Figure 1.4 Computed structures of bare cationic Aun+ clusters and 2D to 3D structural transition.
Source: Reprinted with permission from [55]. © 2019 Royal Society of Chemistry.
materials. Precise control over the edge and topology is of vital importance for controlling the func-
tionality, and heteroatom doping (e.g. doped WS2) also calls for atomic precision strategies [62].
In the semiconductor industry, silicon chips have moved toward the few-nm regime, in which
precise control of the film quality and interface has become a major issue in order to prevent elec-
trical leak in the few-nm transistors [63]. This calls for atomically precise fabrication strategies,
which is vital in advancing toward the 1-nm transistor technology.
1.2 Types of Nanoclusters Covered in This Book
Intense efforts in the past years have led to success in synthesizing Au, Ag, Cu, Pt, Pd, Rh, Al, Fe,
Co, and Ni nanoclusters, as well as alloys. The obtained atomically precise nanoclusters can serve
as new models or platforms for solving many issues of structure and bonding evolution, and thus
enable significant progress in nanoscience research.
This book is intended to provide an overview of the progress in atomically precise nanochemis-
try with a focus on inorganic nanostructures, including metals (e.g. Au, Ag, Cu, Ni, Rh), Zintl
clusters, Ti-oxo nanoclusters, and carbon clusters, as well as catalytic application and assembly of
NCs into functional materials. On a note, other types (e.g. Pdn, [64] Ptn, [65] Aln [66] and cerium-
oxo NCs [42], metallo-rings and wheels [11], supramolecular cages/polyhedrons/capsules [11, 48],
and DNA-templated Aun and Agn NCs [67, 68]) are not covered due to the limitations of the book.
Semiconductor NCs [20–23] are also not covered.
Among the chapters, atomically precise metal NCs (Au, Ag, Cu, Ni, Rh) and their catalytic appli-
cations are discussed in Chapters 2–10. Some other types of NCs, including endohedral metallof-
ullerenes (EMF), GNRs, Zintl clusters, and Ti-oxo nanoclusters, are presented in Chapters 11 to 14.
Finally, Chapters 15 and 16 are devoted to the assembly of metal NCs (Au, Ag, Cu), including their
incorporation into metal organic frameworks (MOFs) toward the fabrication of assembled func-
tional materials.
1.2.1 Atomically Precise Metal Nanoclusters (Au, Ag, Cu, Ni, Rh)
In recent years, atomically precise metal NCs have been intensely pursued. Such NCs may be
divided into three types:
i) Coinage metals, including Au, Ag, Cu, and alloys, which are primarily motivated by the elegant
optical properties of such elements in the form of NCs (c.f. their larger counterparts – plas-
monic NPs in the 3–100 nm range exhibiting distinct SPRs in the visible and near-infrared
wavelength range),
ii) Platinum group metals, including Pd, Pt, Rh, and alloys, which are mainly motivated by their
excellent catalytic properties, and
iii) Magnetic metals, such as Fe, Co, Ni, and alloys, which are primarily motivated by the size-
dependent magnetism from the cluster state to the bulk metals.
Among the types of atomically precise metal NCs protected by various types of ligands (e.g.
phosphines [69, 70], thiolates [71, 72], alkynyls [73], carbenes [74], halides [75], and Stibine [76]),
the gold-thiolate (Au-SR) system is perhaps the most extensively studied one (Figure 1.5). Its larger
counterparts (i.e. plasmonic Au NPs of 5–100 nm) have been widely studied in the past decades
and explored in numerous applications. The success in atomically precise gold-thiolate NCs (tens
to hundreds of gold atoms per core) will help explain the regular NPs in terms of the latter’s surface
structure, assembly, and catalytic mechanism, as well as many other fundamental aspects [10, 77].
In this book, Chapter 2 by Xie’s group summarizes the progress in total synthesis of gold NCs,
including the control over size, structure, composition and ligand engineering, and Chapter 3 by
Wu’s group reviews the advances in the synthesis, characterization, and application of gold NCs
with a focus on the categorization of structural series. The structures of metal NCs constitute the
basis for understanding the functionality and stability of NCs. A theoretical perspective on the
structure evolution and structural design of Aun(SR)m NCs is provided by Xu and coworkers (see
Chapter 4). Among the applications of Au NCs, catalysis (e.g. electrocatalytic water splitting and
CO2 reduction) is summarized in Chapter 5 by Lee’s group, and theoretical simulations on the
electrocatalysis mechanisms are given in Chapter 6 by Tang’s and Jiang’s groups.
While a large body of research focuses on gold NCs, there has also been substantial progress in
Ag NCs (reviewed in Chapter 7 by Zhu’s group), Cu NCs (Chapter 8 by Bakr’s group), Ni NCs
(Chapter 9 by Hayton’s group), and Rh and its alloy NCs (Chapter 10 by Femoni’s group). Some
selected crystal structures of these metal NCs are shown in Figure 1.6.
...... Au25 Au38 Au144 Au246 Au279 Au333 ......
1.0 nm 1.2 nm 1.7 nm 2.2 nm 2.2 nm 2.3 nm
e
Au
25 (SR
)
18 Au
38 (SR h
)24 Au
44 (SR
1
)60
N
(Mole onmeta
Au
246 (SR
llic )80
c
elec ular-like
tron +33 Au atoms
excit single Au279(SR)84
ation
) Metallic
(Plasmon excitation)
Figure 1.5 Atomically precise gold nanoclusters with the transition from nonmetallic Au246 to metallic
Au279. Source: Reprinted with permission from [77]. © 2021 The Authors (Jin and Higaki).
[Ag44(SR)30]4– [Cu25H22(PPh3)12]+
(R omitted)
[Rh33(CO)47]5– [Ni30S16(PEt3)11]0
(CO omitted)
P
S
Ni30 coreshell
Figure 1.6 Examples of atomically precise Ag, Cu, Rh, and Ni nanoclusters with metal─metal bonding.
Source: Adapted from Chapters 7–10.
The types of metal NCs that are discussed in Chapters 2–10 contain a certain number of delocal-
ized valence electrons of metal atoms, such as 2e, 8e, 18e, 20e, 34e, 40e, 58e, 70e, and 92e. These
so-called electronic magic numbers are closely relevant to the stability and properties of the NCs.
Unlike the zero valent Au, Ag, Pt, Pd, and Rh NCs – which can even be in negative (e-rich) states
for Rh atoms [78], Cu NCs tend to be in Cu(I) state or have low numbers of core valence electrons,
such as 2e in the NCs of [Cu25H22(PPh3)12]+ [79], [Cu13{S2CNnBu2}6(CCPh)4]+ [80],
Cu14(C2B10H10S2)6(CH3CN)8 [81], and [Cu61(StBu)26S6Cl6H14]+ [82]. However, upon introducing
hetereometal dopants, the valence electron number could be raised, such as the 10e
[Pt2Cu34(PET)22Cl4]2− [83a] and the 67e [Cu43Al12](Cp*)12 [83b].
Historically, chemists have long been interested in counting the valence electrons, such as
the organic aromaticity rule of 4n + 2 (π electrons) put forth by Hückel in 1931, and the Wade-
Mingos electron counting rules for boron and metal clusters [38, 39] developed in the 1970s, the
superatom electron counts [52] in the 1980s, and so on. More discussions on the counting of clus-
ter valence electrons are provided in Section 1.3.2.
On the other hand, there are also many Au(I), Ag(I), and Cu(I) NCs that have no free valence
electrons, such as the anion-templated Cu(I) and Ag(I) NCs. While these systems are not the focus
of this book, some Cu(I) and Ag(I) NCs are discussed in Chapter 8 and 16, respectively. In
Chapter 8, Dong et al. provides a very systematic summary of the syntheses of Cu(I) and Cu(0)
NCs, whereas Chapter 16 by Wang and Zang focuses on the assembly of Ag(I) NCs for framework
materials, and Chapter 15 by Mandal’s and Sun’s groups summarizes the assembly of Au and Ag
NCs into 3D and 2D crystals.
1.2.2 Endohedral Fullerenes and Graphene Nanoribbons

Nanocarbon has many types, including the fullerenes (Cn), EMFs, carbon nanotubes, graphene
quantum dots, and nanoribbons. Some of them are in atomically precise forms, such as fullerenes
and endohedral fullerenes, as well as certain GNRs.
Since the discovery of C60, carbon clusters have long been of major interest to chemists, physi-
cists, and materials scientists owing to the unique cage structure, superconductivity, and other
unprecedented functionalities [57–60]. In this book, Chapter 11 is devoted to the endohedral
fullerenes (Figure 1.7). Chen’s group has summarized recent progress in EMFs with a monomer,
dimer, and even cluster enclosed in the carbon cage, forming metallofullerenes and clusterfuller-
enes, and the new properties are discussed, such as optical absorption, electrochemical, and mag-
netic properties, as well as the chemical reactivity. Charge transfer from the enclosed metal atom
to the fullerene cage may result in different isomeric fullerene structures. In the case of two metal
atoms enclosed, metal─metal interactions (including bonding and non-bonding) lead to interest-
ing phenomena. The inclusion of more atoms gives rise to clusterfullerenes, such as the enclosing
of metal nitride (e.g. Sc3N), oxide (Dy2O), sulfide (Sc2S), carbide (M2C2, where M = metal), and
carbonitride (Sc3CN) clusters. The configuration of the enclosed few-atom cluster may be rigid
(e.g. M3N) or flexible (e.g. M2C2), and the enclosed cluster may also transfer a certain number of
valence electrons to the fullerene cage.
Fullerenes and doped ones exhibit rich optical absorption peaks in the visible to near-infrared
(NIR) range. The different metal-cage interaction and electron transfers greatly affect the energy
distribution of molecular orbitals of endohedral fullerenes and thus their optical absorption spec-
tra. There are also rich electrochemical properties of endohedral fullerenes, and both the first oxi-
dation and first reduction potentials can be largely varied by the metal atoms in the cage.
In addition to the zero-dimensional (0D) Cn clusters with spherical or spheroidal shape, atomi-
cally precise 2D GNRs are also of major interest (Figure 1.8). Chapter 12 by Yamada and Hayashi
summarizes some recent progress in the on-surface synthesis of GNRs and bandgap engineering
toward transistor applications.
1.2.3 Zintl Clusters

Zintl cluster research constitutes an important branch in the field of inorganic chemistry. Previous
work focused on the main group elements such as Ge, Pb, and Sb. Recent efforts have also investi-
gated transition metals (Figure 1.9), for example, Dehnen’s group carried out a series of work on
endohedral Zintl clusters such as [Th@Bi12]4−, [Co@Sn6Sb6]3−, and double-metal centered [Co2@
Sn5Sb7]3− [34]. Sun’s group recently obtained large sized [Au8Pb33]6− and [Au12Pb44]8− with gold
kernels and lead shells [36]. Chapter 13 by Sun and coworkers have summarized some recent
C60 cage La2@lh(7)–C80 Gd3N@C2(22010)–C78 Sc3CN@lh(7)–C80
Figure 1.7 Structures of C60 and some endohedral fullerenes (the letter colors code the elements).
Source: Adapted from Chapter 11.
(a) (b)
N=
N= 1
1 2
2
3 3
4
5 4
6 5
7
6
7-AGNR 6-ZGNR
Figure 1.8 Types of graphene nanoribbons (GNRs), (a) Armchair type (e.g. 7-AGNR), (b) Zigzag type
(e.g. 6-ZGNR. Source: Adapted from Chapter 12).
[As@Ni12@As20]3– [Sb3Au3Sb3]3– [Co@Sn6Sb6]3–
[Au12Pb44]8– [Au8Pb33]6–
Figure 1.9 Structures of some Zintl clusters (the letter colors code the elements). Source: Adapted from
Chapter 13.
progress in Zintl clusters of group 15 elements (i.e. pnictogens), including homo- and hetero-
metallic clusters. The anionic clusters can be readily isolated from the solutions of corresponding
binary Zintl phase composed of pnictogens and alkali metal salt. The introductions of group 13 or
14 elements or transition metals such as Au and Ag, leads to rich configurations for binary and
ternary clusters, which provide new systems for studying the geometric and electronic properties,
as well as the bonding pattern. Extensive theoretical work on Zintl clusters has been carried out.
The adaptive natural density partitioning method (AdNDP) [84] has been applied to both Zintl
clusters and ligand-protected metal NCs. A comparison of their electronic structures would benefit
a deeper understanding of both types of NCs.
1.2.4 Metal-Oxo Nanoclusters

Metal-oxide nanoparticles such as TiO2 and CeO2 have also received wide interest owing to their
importance in catalysis [17]. Research on the cluster form, i.e. metal-oxo few-atom clusters and
nanoclusters, provides atomically precise models for understanding the surface structure and
Ti16 ring Ti32 ring
Ti42 spherical cage Ti52 dense structure
Figure 1.10 Structures of some Ti-oxo nanoclusters (denoted as Tin, color code: TiO4 = red; TiO5 = purple,
TiO6 = green, TiO7 = blue). Source: Adapted from Chapter 14.
coordination bonding that are involved in regular nanoparticles of the corresponding oxides. There
are many types of metal-oxo nanoclusters, such as Ti-oxo, Mo-oxo, and W-oxo systems [11]. In this
book, Chapter 14 by Gao et al. illustrates the TOC system and the doped ones. Impressive progress
has been made on the study of TOCs in its relatively short history [41, 43], and a variety of structures
have been reported (Figure 1.10), including homometallic and bimetallic TOCs. Such nanoclusters
are quite promising in solar energy utilization for catalysis as well as nonlinear optics [41, 45, 47].
1.3 Some Fundamental Aspects
Many types of NCs are being pursued in different communities, but there has been little commu-
nication between these communities. This book brings together these different research areas
under the umbrella of “atomic precision” for potential stimulations. There are indeed some com-
mon themes or pursuits among the different areas, such as the size dependent structure evolution,
the superatom electronic structure, structural and bonding patterns, and the doping strategy for
tailoring the functionality. Among them, the superatom concept has been pursued across different
research communities such as the metal clusters [56], semiconductor heterostructures [85],
EMFs [60], and Zintl clusters [40] owing to their atom-like orbitals and valency. In this section, we
select some general themes for further discussions.
1.3.1 Synthesis and Crystallization

Atomically precise NCs require precise control over the size, structure, and composition. It is wor-
thy of a comment on the gas phase versus solution phase synthesis. In gas phase preparations,
clusters are formed by condensation of atomic vapor; thus, no chemical treatment such as etching
or size-focusing [10] could be performed in order to achieve uniformity. Thus the gas phase prod-
ucts are typically subject to mass selection by mass spectrometry (MS). In contrast, solution phase
synthesis of clusters and nanoclusters use metal salts or complexes as precursors, which are
1.3 Some unnamental Aspects 13
reduced by a reductant such as NaBH4. During the reaction process, conditions such as tempera-
ture and the ligand-to-metal ratio can be controlled to obtain the target product. The subsequent
purification by solvent extraction or chromatography isolation can give rise to a pure product, then
single crystal growth for structure determination by XRC.
Here we illustrate the solution phase synthesis of atomically precise gold NCs, whose characteriza-
tion involves both MS and XRC. The MS includes matrix-assisted laser desorption ionization
(MALDI) and electrospray ionization (ESI) methods. Among the synthetic methods, the size-focusing
methodology and the ligand exchange-induced size/structure transformation (LEIST) methodology
have been established [86, 87], which have allowed for the synthesis of a series of Aun(SR)m NCs. For
example, the 2.2 nm Au246(p-MBT)80 (where, p-MBT = SPh-p-Me) nanocluster was synthesized by a
two-step “size-focusing” method [13]. In the first step, a polydisperse product in the range of ~10 k to
~70 k Dalton was made by NaBH4 reduction of polymeric Au(I)SR precursors. The second step
involved a size-focusing process: in the presence of excess thiol and under heating conditions, the
initially polydisperse NCs were gradually converged to the most stable product of 56 k Da mass
(Figure 1.11) due to the latter’s high stability under the applied chemical conditions.
Unlike regular NPs that are represented by their average size, atomically precise NCs are reported
by their precise formulas, resembling the case of molecules. Thus, the same sized NCs, no matter
how they were made (e.g. by different methods or laboratories), must possess the same formula.
Thus, there is no concern for size heterogeneity. The NCs are also of molecular purity (e.g.
>99%) [72], resembling molecular compounds, and they adopt the same structure (except the case
of isomerism). Among the characterization methods, MS and XRC play vital roles.
Both MALDI- and ESI-MS methods are widely used in nanocluster analysis. In MALDI analysis,
some ligands are often knocked off, hence, the precise mass of NCs is not obtainable by MALDI,
but the wide range scan can provide important information on the sample purity. Compared to the
Figure 1.11 Size-focusing synthesis of 10k 24k 31k 56k 71k

Au246(p-MBT)80 monitored by MALDI-MS. During the
size-focusing process, the initially polydisperse
product gradually converges to the most stable 56 k
Dalton species corresponding to Au246(p-MBT)80. 0h
Source: Reprinted with permission from [13].
© 2016 American Association for the Advancement
of Science. 0.5 h
1.5 h
3.5 h
5h
7h
8h
9h
10 h
0 20 40 60 80 100 × 103
m/z
3+
4+
2+
10000 15000 20000 25000 30000

m/z
Figure 1.12 ESI-MS analysis of Au246(p-MBT)80. The peaks correspond to the 4+, 3+, and 2+ ion sets of
Au246(p-MBT)80 (MW = 58 309). Source: Reprinted with permission from [13]. © 2016 American Association
for the Advancement of Science.
MALDI, ESI is a much softer ionization technique and is thus more suitable for the formula deter-
mination. Based on the precise mass determined by ESI, one can easily deduce the formula. For
example, the above 56 kDa product was deduced to be Au246(p-MBT)80 (Figure 1.12). In this analy-
sis, in-source ionization led to the 2+, 3+, and 4+ molecular ion peaks (note: the 1+ peak is beyond
the ESI detector’s mass range, up to m/z 40 k only, whereas MALDI can go to a much higher range).
With the molecular mass (MW = 58 309) determined, one can deduce the number of gold atoms
(n) and ligands (m) by applying conditions of (i) n > m (this is owing to the metal─metal bond
formation in NCs, whereas the AuISR complex features n = m), and (ii) accurate match between
the formula mass and the ESI-determined one. Therefore, high precision ESI is indispensable in
order to precisely determine the cluster formula. The as-determined formula should also be con-
firmed by XRC analysis. When both analyses are consistent, one can be confident about the for-
mula, especially for large sizes (>100 gold atoms).
For structural analysis, the most reliable and popular method is the single-crystal X-ray diffrac-
tion analysis (i.e. XRC) [11]. Typically, the single crystal growth is performed by diffusion of an
antisolvent (e.g. acetonitrile) into a solution of the NCs (e.g. in toluene). The total structures of
NCs reveal not only the core (i.e. the arrangements of metal atoms) but also the surface structure
(i.e. the arrangements of ligands and bonding between the ligands and the core); see an example
in Figure 1.13. Intense research over the past years has led to the successful syntheses and struc-
ture determinations of a series of sizes of Au-SR NCs (see Chapter 3).
In addition to size control, ligand engineering is also important because the ligands play some
critical roles in photoluminescence, catalysis, and biomedicine [10, 18]. Xie’s group [88] reported
the incorporation of two or multiple types of thiolates into the ligand shell of Au25, such as the
thiolates containing carboxylic, hydroxyl, or amine groups (Figure 1.14a). To obtaining a ligand
shell with positive charges, Ishida et al. synthesized Au25(SR+)18 with cationic ligands such as (11-
mercaptoundecyl)-N,N,N-trimethylammonium, HS-(CH2)11N(CH3)3+, and their recent work has
also demonstrated a surface reaction route for obtaining such fully cationized NCs
(Figure 1.14b) [89a]. Clickable azide-functionalized-Au25 was reported by Gunawardene
et al. [89b]. Such NCs provide new opportunities for surface reactions. Xie’s group carried out
impressive work to obtain insights into the nanocluster growth mechanisms in aqueous systems by
X-ray crystallography (single crystal X-ray diffraction)

Au246(SPh-p-CH3)80
Atomic resolution (<1 Å)

2 nm
Figure 1.13 Crystallization of atomically precise nanoclusters and total structure determination by X-ray
crystallography. Source: Redrawn from the cif file [13] of Au246(SPh-p-CH3)80.
(a) HS HS
O NH2
HS
HS OH O OH
Au25 HS
HS
OH O
R ≤ 3 hrs HS
H2O OH O
NaOH NaBH4 Reduction
HAuCl4
S
Thiolate Au HS OH
Etching
ligand n O O
Au(l)-Thiolate complexes
HS
HS OH OH
Au25 NH2
HS NH2
O O O
H
N
HO N OH
H
O
NH2
(b) N N N
+ N +
N + N+
N N
N + N +
N N
N Menshutkin N
S S S
+ S S S +
N S S reaction N S S
S S S S
S S N S S N
S
Au
25 S +
S
Au
25 S +
N N
S S S S
SS S N SS S N
S S +N S S
N +
N N
N +N +
N N
N
N
+N N +
N +N +
[Au25(4-PyET)18 ]– [Au25–1(4-PyET-CH3+)x(4-PyET)18-x]x-1
X≈18
Figure 1.14 Ligand engineering for the Au25(SR)18 nanocluster, (a) through NaOH-assisted NaBH4
reduction method, and (b) through surface reaction for transformation into fully cationized NCs. Source:
Panel A adapted from Chapter 2; panel B, reprinted with permission from [89a]. © 2021 American
Chemical Society.
ESI-MS analysis, including the details of Au25(SR)18 formation, intercluster metal exchange,
surface motif exchange, isomerization, and size conversion (see more discussions in Chapter 2).
While noble metal NCs (Au, Ag, Rh, etc.) are typically synthesized by chemical reduction of
their salts or complexes, the cases of Cu and Fe/Co/Ni NCs with zero valence (i.e. the metal─metal
bond formation) become challenging and have only met with very limited success. Hayton’s
group [79] earlier reported [Cu25H22(PPh3)12]+ (with partial Cu(0)) and recently also tackled the Ni
nanoclusters. While the NiII(SR)2 precursor is hard to be reduced, the use of [Ni(1,5-cod)2] as the
Ni source and PEt3 as a supporting ligand led to the successful synthesis of Ni30S16(PEt3)11 and
structural characterization [90], which provides new opportunities for pursuing atomically precise
magnetic NCs. Compared to the solution phase syntheses of metal and Zintl as well as Ti-oxo NCs
(Chapters 2–10, 13, and 14), the preparation of endohedral fullerenes typically adopts gas phase
methods (Chapter 11), and GNRs can be prepared by solution phase organic chemistry or on-
surface synthesis, both at atomic precision (Chapter 12).
1.3.2 Structural and Bonding Patterns

Since much work has been reported on gold NCs, here we focus on the gold-thiolate system. Based
on the reported X-ray structures of gold NCs, there are several major types of core structures [10],
which are the icosahedral (Ih), decahedral (Dh, including the Marks and Ino types, denoted as m-
Dh and i-Dh), face-centered cubic (fcc), tetrahedral Au4 network, hexagonal close packed (hcp),
body-centered cubic (bcc), and mixed phases (Figure 1.15a). It is noteworthy that bulk gold is fcc;
(a) Types of core structures 9

Au 27
4
Au 38 Au 14
Ih nic
Au 13
3 smo
Pla
bcc Au 30 Au 92
hcp Au 38 u lar
Au 52 # of A Mol
ecu
Au 25 Au 44 s ing
rea
Au 36 Inc
Ih Au 28
Au 49
Au 23 Au 38 Au 24
6
fcc Au 13
0
ed
Mix ses Au 10
3
pha Dh
Au 10
2
(b) Types of surface structures
Au(SR)2 Au2(SR)3 Au3(SR)4 Au4(SR)5 Au8(SR)9
Figure 1.15 Types of core structures (a) and surface-protecting motifs (b) in Aun(SR)m nanoclusters.
Source: Panel A: Reprinted with permission from [91]. © 2020 American Chemical Society. Panel. B: adapted
from Chapter 3.
thus, the observations of hcp and bcc phases in gold NCs are quite intriguing. Different from the
fcc/hcp/bcc types that are crystallographic (i.e. possessing translational symmetry), other struc-
tural types such as Ih and Dh as well as the Au4 network type are noncrystallographic because the
presence of five-fold symmetry or other factors destroy the translational symmetry, but they still
possess molecular symmetry, which endows high stability to such noncrystallographic NCs. It is
noteworthy that Wu’s group reported quite a number of mixed-phase NCs [92], including Au46(m-
MBT)26, Au48(m-MBT)26, Au49(DMBT)27, and Au67(SCH2Ph)35 (more discussions in Chapter 3).
Another important aspect pertains to the surface structures that cannot be mapped out by elec-
tron microscopy but can be readily mapped out by XRC analysis. A traditional view on the nano-
particle structure is a polyhedral core (or truncated one) with a protecting layer of organic ligands.
But, surprisingly, the X-ray structures of Aun(SR)m revealed that some gold atoms are partitioned
into the surface-protecting layer, forming unique staple-like motifs (Figure 1.15b) such as the mon-
omer, dimer, trimer, and tetramer, as well as the plain bridging thiolate (–S(R)–, without any gold
atom incorporated). The x-mer staples incorporate an x number of gold atoms and can be expressed
as Aux(SR)x + 1, with x = 1–4 [10]. An octameric staple motif, Au8(SR)9, has also been found in the
Au21(S-Adm)15 structure [93]. In small sizes of Aun(SR)m, ring-like motifs are also present, includ-
ing the octameric Au8(SR)8 ring (as opposed to the octameric staple) in Au20(S-Ph-p-tBu)16 [94a]
and hexameric Au6(SR)6 ring in Au28(S-Adm)22 [94b].
The growth pattern of NCs reveals the evolution of structure with increasing size. While early
research only reported some scattered sizes without mutual relationships, later work indeed
revealed intriguing growth patterns, including 1D, 2D, and box-type addition growth. In these pat-
terns, the fundamental building blocks are the Au4 tetrahedron, fcc-Ag14 cube, and M13 icosahe-
dron (or cuboctahedron), as well as M5 decahedron, where M = Au or Ag. Below we illustrate a few
series of NCs.
One-dimensional periodic growth of NCs was first discovered in the series that is composed of
Au28(TBBT)20, Au36(TBBT)24, Au44(TBBT)28, and Au52(TBBT)32, where TBBT = 4-tert-butylbenzen-
ethiolate (SPh-tBu) [95]. In this series (Figure 1.16), a uniform increment of Au8(SR)4 was found,
and X-ray structures revealed a double helical extension of Au4 units. Theoretically, groups of
Pei, Gao, and Zeng provided insights on this series and also predicted some longer 1D NCs such as
Au60(SR)36, Au68(SR)40, and Au76(SR)44, [96, 97] but no experimental success yet. The HOMO-
LUMO gap shrinks with increasing size (i.e. length) but does not reduce to zero, rather, it con-
verges to 0.7 eV [96]. On a note, Wu and coworkers [98] also found Au56(TBBT)34 with a helical
growth in relation with Au52(TBBT)32.
Au28(SR)20 Au36(SR)24 Au44(SR)28 Au52(SR)32 Au60(SR)36 Au68(SR)40 Au76(SR)44
Structure solved Structure predicted
Figure 1.16 One dimensional periodic growth of Au8n + 4(SR)4n + 8 nanoclusters (n = 3, 4, 5, 6, etc.). Color
labels: golden = Au, red = S, carbon tails omitted for clarity. Source: Reprinted with permission from [96].
© 2016 Royal Society of Chemistry.
One-dimensional growth
Au28(SR)20 Au36(SR)24 Au44(SR)28 Au52(SR)32
a1 (0.00) b1 (0.00) c1 (0.00) d1 (0.06)
a2 (0.25) b2 (0.11) c2 (0.63) d2 (0.00)
a3 (0.24) b3 (0.50) d3 (0.12)
Two-dimensional growth
Figure 1.17 Relation between 1D growth (blue arrows) and 2D growth (green arrows) of Au8n + 4(SR)4n + 8
nanoclusters. Each vertical column shows the isomers for the corresponding size (e.g. a1, a2, and a3 for the
Au28(SR)20 formula; the relative energy (eV) for each isomer is shown in parentheses). Source: Reprinted
with permission from [99]. © 2020 The Authors (Liu et al.)
Based on the Au28 to Au52 1D growth pattern, Gao et al. further predicted a 2D growth pattern
(Figure 1.17, green arrows) and it was experimentally verified [99]. The pattern shows that starting
from the a3 isomer of Au28(SR)20, b2 of Au36(SR)24 can be obtained via a 2D growth. Experiment by
Zhu’s group indeed obtained the b2 isomer using 2,4-dimethylbenzenethiol (DMBT) as the ligand
via a two-step size-focusing method. Both b1 and b2 isomers were produced in one pot, but chro-
matography isolated them, and the structure of b2 was determined to be the same as predicted [99].
Based on the superatom network model, AdNDP analysis on the Au208+ kernels of b1 and b2 iso-
mers showed that the 12 valence electrons are equally distributed on the six Au4 tetrahedra (2e
superatoms), that is, a type of 4c-2e bond in each tetrahedron. Overall, this combined theory/
experiment work is quite insightful in revealing the growth patterns. Future work may lead to the
synthesis of other isomers under each formula (Figure 1.17) by designing suitable ligands and
other experimental conditions.
In addition to the 1D helical growth and the 2D pattern, Chapter 3 by Gu and Wu provided an
excellent summary of other patterns based on the Au4 and Au3 units such as the quasi-linear Au4
tetrahedron growth by sharing one vertex, Au3-additive growth, and Kekulé-like ring growth, as
well as icosahedral Au13 based growth. They also discussed the series of NCs with “homo-kernel
hetero staples,” i.e. the same kernel can be protected by different surface staple motifs, such as the
pair of Au28(TBBT)20 and Au28(S-c-C6H11)20 NCs with the same Au14 kernel but different motifs for
protection, as well as the pair of Au44(TBBT)28 and Au42(TBBT)26 NCs with the same Au26 kernel
but different numbers of dimeric and monomeric motifs (though identical types) [100]. These
results motivated Xu et al. [101] to develop a new method for theoretical structural design of
Aun(SR)m NCs by redistributing the staple motifs on the known Au kernel structures, hence, a
(a) (b) (c) (d)
(e) (f) (g) (h)
1 (1×1×1) 21 (2×1×1) 22 (2×2×1) 23 (2×2×2)
Figure 1.18 “Box”-addition growth pattern in a fcc series of Agn NCs: (a) [Ag14(SPhF2)12(PPh3)8] (denoted
1), (b) [Ag23 (SC2H4Ph)18(PPh3)8] (21), (c) [Ag38(SPhF2)26(P-nBu3)8] (22), (d) [Ag63(SPhF2)36(P-nBu3)8]+ (23), and
their corresponding models (e−h) depicted as the idealized fcc box addition sequence. Color codes: blue
and light blue sphere = Ag; red sphere = P; yellow sphere = S; green = F; gray = C. Source: Redrawn
from [103] and [104]. © 2017 American Chemical Society and 2018 The Authors (Liu et al.).
prediction of new stable Aun(SR)m nanoclusters without the need of the demanding global-
minimum search (see Chapter 4). Chapter 4 (Xu et al.) summarizes an additional series of periodic
NC growth. It is also worth noting that Pei’s group reported a “gold-atom insertion, thiolate-group
elimination” rule for the evolution from Au28(SR)20 to Au29(SR)19 to Au30(SR)18, [102a] and a 2D
growth pattern for the evolution from Au44(SR)28 to Au68(SR)36 to Au92(SR)44 [102b]. These are
experimentally supported [71c, d].
In the Agn research, groups of Zheng [103] and Li [104] identified a box-addition type of growth
pattern in the series composed of Ag14, Ag23, Ag38, and Ag63 (Figure 1.18). These NCs feature the
fcc Ag14 unit and are protected by binary ligands (thiolates on the facets and eight phosphines on
the corners). Zheng’s group also reported a series of [Au12 + nCu32(SR)30 + n]4− (n = 0, 2, 4, 6) with
surface motif exchange while retaining the kernel structure (Au12@Cu20) [105].
To understand the structure evolution and unify the reported Aun(SR)m structures, groups of Xu,
Gao, and Zeng have made great efforts. A grand unified model (GUM) was established in 2016 [106],
which offers insights into structure stability and patterns, as well as predictions of new NCs. This
model was inspired by the quark model in particle physics, in which a proton or neutron is com-
posed of three quarks, as well as the tetraquark containing two quarks and two antiquarks, whereas
in gold NCs, the elementary blocks are the triangular Au3+ (analogous to the proton/neutron) and
the Au42+ (analogous to the tetraquark), each block holding two valence electrons. The gold atoms
in each elementary block may be of three “flavors,” Au(1e), Au(0.5e) and Au(0e), in other words,
three different valence-electron states. The icosahedral Au13 can be viewed as a secondary building
block constructed from the Au3 to Au4 elementary ones. Here, it is worth noting that the valence
electrons refer to those that are not bonded (or localized) by surface ligands, rather, being in
metal─metal bonds. Given the delocalization nature of metal─metal bonds, some authors may use
the term of free valence electrons, but the term “free” should not be mistaken as the free electrons
in the metallic or plasmonic state, because in NCs of smaller than Au279(SR)84, the strong quantum
Au38Q
(a)
=3× +6× +
0.5+
(b) 0.5– 0.5–
= = + × + ×
× = × 0.5+
= I46 + T5 + 2 × Δ5
Au38T
(c)
= +3 × + 3× +2 × +
0.5+
(d) 0.5– 0.5–

+
+ × × ×
= × = 0.5+
= I46 + T5 + 2 × Δ5
Figure 1.19 The GUM-guided structural dissection of Au38Q (a and b) and its isomer Au38T (c and d). Color
code: magenta and dark yellow represent Au atoms with 1e and 0.5e valence states, respectively; dark
green represents S atom. R groups are omitted for clarity. Reprinted with permission from [110]. © 2018
American Chemical Society.
confinement effect leads to discrete orbitals on which the delocalized valence electrons occupy;
they are not free electrons; [107–109] otherwise, gapless excitations (i.e. plasmons, as opposed to
excitons) would occur in sizes below Au279(SR)84 [107]. With the GUM, a plethora of complex and
seemingly unrelated structures of gold NCs have been deciphered, and the structure evolution was
understood [106]. Using Au38(SR)24 as an example, its structure can be dissected as shown in
Figure 1.19, and the core isomerism can also be rationalized [110]. The stabilities of NCs originate
in the local stability of each building block, and the growth of NCs can be viewed as a sequential
addition of the building blocks, as opposed to the traditional view of addition of individual atoms.
The stability of Aun(SR)m NCs has also been studied in terms of thermodynamics. Based on the
experimental structures, Mpourmpakis and coworkers reported a thermodynamic stability model
for the Aun(SR)m NCs, [111] in which they identified that when the binding energy (BE) of shell-
to-core equals the cohesive energy (CE) of the core, stable NCs result (see the “parity line” in
Figure 1.20). This energy balance is indeed maintained over a large size range of Au NCs from the
molecular (e.g. Au18, with large Eg ~ 1.7 eV) to the metallic regime (Au279, Eg of meV supposedly),
even extendable to the bimetallic NCs [111].
The particular stability of certain sizes of NCs is interesting, which typically originates from two
major factors, the geometric and electronic stabilities [51, 52]. The discussions in this section have
illustrated the types of atomic structures of NCs; high-symmetry structures typically lead to high
stability. Here we further discuss the electronic factor, which contributes to the stability and affects
the geometric structure (e.g. by the Jahn-Teller effect in superatomic 1P state of bimetallic M25 and
–70
E
C
=
BE
Au146(SCH3)57
–60
Shell–to–core BE (kcal mol–1)
Au102(SCH3)44 Au279(SCH3)84
Au246(SCH3)80
Au40(SCH3)24
–50 Au38S2(SCH3)20 Au52(SCH3)32
Au38(SCH3)24t
Au38(SCH3)24q
Au18(SCH3)14
–40
Au30S(SCH3)18
Au36(SCH3)24
Au28(SCH3)20
–30
Au24(SCH3)20
Au20(SCH3)16
–20
–20 –30 –40 –50 –60 –70
Core CE (kcal mol–1)
Figure 1.20 The origin of thermodynamic stability of Aun(SR)m nanoclusters (BE: binding energy of shell to
core; CE: cohesive energy of the core). Source: Reprinted with permission from [111b]. Copyright 2019 Royal
Society of Chemistry.
homogold Au25 NCs, [112] in contrast with the Jahn-Teller effect of atomic d state in transition
metal complexes). The electronic structure of NCs is also closely relevant to the bonding pattern.
It may be worthwhile to start with the electronic structure of elements in the periodic table. The
inert gases (e.g. He, Ne, Ar, Kr, Xe) are chemically inert due to electron shell closing, and the stabil-
ity numbers are 2e, 10e, 18e, 36e, and 54e. Shortly after the elucidation of the electronic structure
for elements in the 1910s–1920s, Sidgwick [113] developed an electron counting scheme for metal
complexes – for example, Ni(CO)4 possesses a total of 36e, that is, 28e (Ni) + 2e × 4 (CO) = 36e,
hence, it is stable because of the same electron number as that of Kr. The octet rule and the
18-electron rule are well known in inorganic chemistry for structure and reactivity predictions.
Both rules describe the tendency of the central metal atom (or ion) to achieve the noble gas elec-
tron configuration in the valence shell, i.e. ns2 np6 or ns2 np6 (n−1)d10 (here, n is the valence shell
number). Complexes with unfilled (n − 1)d orbitals can bind more ligands and exhibit higher
reactivity.
The concept of chemical bonding is of central importance in chemistry and the cluster research
has significantly expanded the concept. Here we briefly outline the evolution from conventional
bonds to new types in boron and metal clusters. In the 1910s, Lewis discussed the covalent bond as
a pair of electrons shared by two atoms (“2c-2e”), where, “c” = center [29]. But this concept was
later challenged by boron clusters due to boron’s electron-deficient nature. New concepts such as
3c-2e, multi-center bonds and 3D aromaticity were put forth then. Based on the structures of boron
clusters, Williams systematically described the deltahedral structural pattern in 1971 and classified
the boron clusters as three categories (i.e. closo-, nido- or arachno-) according to their formu-
las [114]. Wade [115] explored the concept of skeletal electron pair (SEP) for cluster bonding and
rationalizing the shape of borane clusters. For example, the icosahedral B12H122− cluster (50e total)
with high stability possesses 13 SEPs (or 26e by the 2n + 2 rule, that is, 2e × 12 [B atoms] + 2 = 26e),
which are highly delocalized on the icosahedral shell. Such σ-aromatic bonding is regarded as
spherical aromaticity [116], similar to the 2D case (e.g. π aromatic bonding in benzene).
Mingos [117] also introduced the SEP concept into gold-phosphine clusters. The relationship
between the structure and electron count in gold clusters was understood in terms of the overlap
of the radially directed s/dz2 hybrids on each gold atom [118]. Several rules were summarized
(called Wade’s or Wade-Mingos rules), including:
i) The closo-type of clusters with n vertices has 2n + 2 skeletal electrons (or n + 1 SEPs).
ii) The nido-type, which is derived from the closo parent by removing one vertex, should have
2n + 4 electrons.
iii) The arachno-type should possess 2n + 6 electrons since this type has 2 missing vertices.
The Wade-Mingos rules – which rationalized the valence electron counting and structure of
polyhedral boranes and metal-phosphine clusters – have been introduced into broader types of
metal clusters and Zintl chemistry as well. For example, according to the 14n + 2 rule, an icosahe-
dron gives rise to 170e (i.e. 14 × 12 + 2 = 170e, where n the number of vertices for an icosahedron,
excluding the central atom). For metal carbonyl clusters such as the [Rh12E(CO)27]q− (where
E = Sn with q = 4, and Sb/Bi with q = 3), one obtains 170e by counting Rh 9e, 4e for Sn (or 5e for
Sb/Bi), 2e for each CO, and the charge q [78]. In Zintl clusters, cage clusters of group 14 also fit well
into the rule of 4n + 2 (Note: Main group elements have no d electrons; hence, 10n less in the elec-
tron count), [34, 37] such as closo-Ge102− and Pb122−. The Pb122− cage possesses 4n + 2 = 50e, con-
sidering that Pb is not a transition metal and has no d electrons for metal─metal bonding, hence,
12 × 10e = 120e less than the 170e count for shell closing in transition metal clusters [78].
With the concepts of aromaticity and multicenter delocalized bonding, the closo-type Ge102− and
Pb122− can be considered as 3D aromatic. In endohedral lead-based Zintl clusters, the 4n + 2 rule
also explains the particular stability of the 60e Zintl clusters of [M@Pb12]q− (M = Ni, Pd, Pt, q = 2;
M = Co, Rh, Ir, q = 3) and the 58e [Mn@Pb12]3−, in which both the M (d10) and the closo-[Pb12]2−
cage acquires closed-shell configurations. The 62e [Au@Pb12]3− is also in line with the 4n + 2 rule.
In the analysis of bonding pattern of Zintl clusters, for example, Sn56− can be understood as classi-
cal Lewis 2c-2e bonds and three delocalized 5c-2e bonds (Figure 1.21), which is indeed similar to
the case of organic C5H5−. The prismatic tri-layered [Sb3Au3Sb3]3− can be considered as π aromatic,
(a) (b)
Structure of Sn56– Five lone pairs Five 2c-2e Sn-Sn Structure of C5H5– Five 2c-2e C-H Five 2c-2e c-c
on Sn atoms σ-bonds σ-bonds σ-bonds
ON = 1.93 |e| ON = 1.98 |e| ON = 1.98 |e| ON = 1.98 |e|
Three 5c-2e π-bonds Three 5c-2e π-bonds

ON = 2.00 |e| ON = 2.00 |e|
Figure 1.21 Bonding pattern of (a) Sn56− and (b) C5H5− involving multicenter-2e bonds (computed by the
adaptive natural density partitioning (AdNDP) algorithm). Source: Adapted from Chapter 13.
and the top or bottom Sb3 triangle achieves a total of 15 valence electrons and involves 3c-3e π-
bonds (three of such bonds) within the layer. More discussions can be found in Chapter 13.
In the 1980s, research on gas phase Nan clusters led to another important concept now called super-
atoms, that is, the particularly abundant Na8, Na34, Na58, and Na92 sizes, which adopt electron shell
structures of closed forms, such as 1S2 1P6 (8e total) for Na8 [52]. This picture was later confirmed in
extensive research on other types of metal clusters [50]. The electron configuration of superatomic
clusters leads to the metal core valence electrons filling as in the following sequence [119]:
1S2 1P6 1D10 2S2 1F14 2P6 1G18 2D10 1H22 3S2 2F14 1I26 3P6 1J30 2G18 3D10 4S2 1K34 2H22 . . .
Note that the sequence was constructed based on an electron in a spherical potential without con-
sidering any electronic correlation or other effects; thus, the sequence of higher levels may differ
from other theoretical treatments [50, 56], such as the jellium model or with the exchange-
correlation incorporated. Different treatments lead to different degeneracy of high-energy orbit-
als such as I, J and K, hence, various magic numbers of electron shell closing, but the lower
numbers such as 2e, 8e, 18e, . . . are quite robust regardless of different treatments. With the orbital
sequence, electron configurations for 34e, 40e, 58e, etc. can be constructed readily. Castleman and
coworkers carried out much work on the reactivity of gas phase Aln superatoms, such as the highly
reactive 39e (open-shell) Al13 and the insert Al13− of 40e (shell closing) [120].
A modified superatom model has been introduced into the ligand-protected metal NCs [121]. In
consideration of the fact that some ligands (e.g. thiolate) form 2c-2e bonds with the metal core
atom(s), some valence electrons of metal atoms are localized and these do not participate in the
delocalized metal─metal bonding. The number of metal valence electrons being localized by each
type of ligands is listed in Table 1.1, in which ligands such as phosphines do not consume metal
electrons due to dative bonding with metal atoms. With the superatom model, the electron con-
figuration of some NCs can be rationalized; for instance, Au25(SR)18− [121, 122] possesses 25(Au
6s1) – 18(SR) + 1 (charge) = 8e, hence, a 1S2 1P6 configuration and accordingly high stability due
Table 1.1 Localization of metal core valence electron(s) by surface ligands in the
superatom model. Note that the electron counts for ligands differ in various models.
Number of electrons
Ligand localized by ligand
Phosphine (PPh3, PR3) 0

Carbonyl (CO) 0
Thiolate or thiolato (-SR) 1
Dithiolate, e.g. 1,3-benzenedithiolate (-S- CR2-S-) 2
Dithiocarbamate (S2C-NR2) 1
Dithiophosphate (S2P(OR)2) 1
Halide (−Cl, −Br) 1
Alkynl (CCPh, CCR) 1
Amine (−NH2, −NHR) 0
Carboxylic group (COO−) 1
NHC (nitrogen-heterocyclic carbene) 0
Hydride (H−) 1
S (bare), Se (bare) 2
to shell closing. Similarly, Au102(SR)44 [123] possesses 58e with a configuration of 1S2 1P6 1D10 2S2
1F14 2P6 1G18, hence, high stability by shell closing. Overall, the stability of Au25(SR)18− and
Au102(SR)44 was well explained by electron shell closing (plus their high symmetry geometric
structures of spherical shape [122, 123]), but some other Aun(SR)m NCs could not be explained by
the superatom picture, for example, Au38(SR)24 with 14e [124].
The superatom model was also used in Zintl clusters [37d]; for example, a celebrated Zintl clus-
ter is the fullerene-like [As@Ni12@As20]3− cluster; its geometric structure consists of an As-
centered Ni12 icosahedron which is enclosed in an exterior As20 pentagonal dodecahedral shell [35].
Theoretically, a charge distribution analysis revealed a pattern of [{As@Ni12}3−@{As20}0], with the
kernel possessing superatomic 1S21P62S2 electron configuration [40].
It is also of interest to discuss the trio NCs of 8e, among which the Au25(SR)18− and Au28(SR)20
both possess 8e and can be viewed as 1S21P6 (Figure 1.22), but Au23(SR)16− (also 8e) is not the case,
and its electron configuration should be viewed as 1S21P41D2 (Figure 1.22) [125]. In addition, the
neutral Au25(SR)180 should be 1S21P5, hence, being open shell and thus magnetic [126]. Unlike
common radicals being short lived, Au25(SR)180 exhibits high stability and longevity and is similar
to the anionic form, which came as a surprise [126]. The facile conversion of Au25(SR)18− to
Au25(SR)180 [127] implies that the 1P6 electrons are not as tightly bound as expected, which is dif-
ferent from the case of atoms (e.g. Ne atoms being highly insert due to 2s22p6 electron shell closing
and tight binding). In addition, the case of spherical Au133(SR)52 is 81e, rather than the expected
70e or 92e for shell closing; the 1H open shell implies magnetism, which has indeed been con-
firmed by experiment [128]. Similar to Au25(SR)180 (7e), the Au133(SR)520 “radical” is also very
stable [128].
To go beyond the superatom model, Yang and Chen [129] put forth a “superatom network”
model in which Au4 (2e) or Au13 (8e) superatoms serve as building blocks for constructing
superatom-based supermolecules such as Au24(SR)20 and Au38(SR)24. The fcc series (Au28, Au36,
Au44, Au52) cannot be explained by the superatom model, but the superatom-network model (with
Au42+ units) indeed explains this series well [96, 97, 130]. The supermolecule picture also explains
the 2D pattern of Au4 units [99, 125, 130]. The discovered new bonding patterns are quite intriguing.
Au135+ Au146+
in Au23(SR)16– in Au28(SR)20
Au104+
in two Au21(SR)15
Au73+
in Au20(SR)16 1D 1P
Basic Units and MOs

1P 1P 1P 1P
ϕ(Tetra)
Au42+ 1P 1P 1P 1P 1P
ϕ(Tri)
Au3+ 1S 1S 1S 1S 1S
2e 4e 6e 8e
N1 N2
ψ(1P) = 0.71[ϕ(Tetra) – ϕ(Tetra)] φ(1S,1P,1D,...) = Σ ciϕ(Tri) + Σ cjϕ(Tetra)
ψ(1S) = 0.71[ϕ(Tetra) + ϕ(Tetra)] i=1 j=1
Figure 1.22 Electron density diagrams of the valence MOs of the Au cores in 2e, 4e, 6e, and 8e clusters.
Source: Reprinted with permission from [125]. © 2019 American Chemical Society.
New types of bonding have also been found in the endohedrally doped fullerenes. For example,
Dy2@C80 shows the presence of a single-electron Dy─Dy bond (2c-1e), that is, Dy-e-Dy. In dimetal-
lofullerenes, the nature of metal─metal bonding inside a cage could be fundamentally different
from the case of isolated M─M, because the enclosed case depends on the cage size and structure.
More discussions can be found in Chapter 11. It is worth noting that the endohedral Zintl clusters
containing a metal dimer, such as [Pd2@Ge18]4−, [37b] is of interest for a comparison with the
dimetallofullerenes for insights into the bonding and electronic properties. Such crossing-
community efforts should be fostered in future work, which is indeed one of our motivations for
organizing this book by bringing together various communities under the common umbrella of
“atomic precision.”
Overall, the cluster research on boron, Zintl, and metal NCs has significantly extended the
chemical bonding concept. Beyond the classical 2c-2e bonding, many new types (e.g. 2c-1e, nc-2e,
and nc-me) have been put forth. Spherical aromaticity has successfully explained the stability of
cage structures. The discovered 1D and 2D bonding patterns in Aun(SR)m NCs are quite intriguing.
The development of electron-counting rules [118, 131] may accommodate broader types of clus-
ters. In future work, new structures are expected to further push the concept of bonding in areas of
atomically precise metal NCs (homo- and hetero-metallic ones), endohedrally doped clusterfuller-
enes, and Zintl clusters (homo- and hetero-metallic types). The unusual bonding behavior will also
lead to new functionalities of such materials.
1.3.3 Transition from Nonmetallic to Metallic State: Emergence of Plasmon

The advent of atomically precise nanochemistry opens exciting opportunities for addressing some
longstanding questions, such as the nonmetal-to-metal transition over the size evolution. The tran-
sition in bulk states of elements in the periodic table is relatively straightforward, that is, bandgap
Eg = 0 for metals and nonzero for nonmetals. However, nanoclusters are finite systems and the Eg
value exhibits size dependency. Then, questions arise: At what size does the metallic state emerge?
Would the nonmetal-to-metal transition be smooth or abrupt? Given the difficulties in measuring
millielectronvolt (meV) gaps [132], a more convenient method is to probe the size at which plasma
emerges in a metal nanocluster. When the plasma state is formed in a particle, a collective excita-
tion of free electrons will give rise to SPRs, which can be spectroscopically probed. For spherical or
nearly spherical Au nanoparticles, a single SPR peak is exhibited. Next, we briefly discuss some
progress in addressing the transition from nonmetallic to metallic state in gold NCs.
Small NCs exhibit discrete electronic energy levels, such as the case of Au25 (Figure 1.23), which
is caused by ultrasmall size or quantization effect. With increasing size, the energy level spacing
becomes smaller and eventually the HOMO-LUMO gap should disappear; accordingly, the metal-
lic state is formed. Recent success in attaining Aun NCs over the size regime of hundreds of atoms
has permitted us to address this fundamental question.
Here we illustrate two critical sizes, Au246(SR)80 and Au279(SR)84, both being ~2.2 nm core diam-
eter. The electronic properties are closely related to the particle shape, thus, their structures were
first analyzed by XRC. It was revealed that Au246 is nearly spherical, [13] with metal core diameter
of 2.2 nm and overall diameter (including the ligand shell) of 3.3 nm. The Au246(SR)80 structure can
be divided into four shells. The kernel is a three-shell Au116 Ino decahedron (i-Dh) that exposes
{111} facets at the top/bottom poles and {100} facets at the waist (Figure 1.24a). The fourth shell is
composed of 90 gold atoms (Figure 1.24b, magenta), which rounds up the particle into a sphere.
The surface layer (Au─S interface) contains various types of motifs, including the plain bridging
─S─, gold-containing monomeric ─S─Au─S─ staples, and dimeric ─S─Au─S─Au─S─ staples
(Figure 1.24c), all of which adapt to the facets and grooves on the Au206 core. Hence, the Au206 core
(a)
0.6
0.5
0.4
Absorbance
0.3 c
b
0.2
0.1 a
0.0
400 600 800 1000
Wavelength (nm)
(b)
Au(sp) S(3p)
–3 Au(d) others
ag (1) LUMO+2
–4 ag (3) LUMO+1
ag (2) LUMO Quantized

–5
E(eV)
sp-band
a b c
–6
au (3) HOMO
ag (2) HOMO-1
–7 au (3) HOMO-2
ag (3) HOMO-3 d-band
HOMO-4
ag (1) HOMO-5
–8 au (3)
Figure 1.23 Quantization of the electronic structure in [Au25(SR)18]–. (a) UV–vis absorption spectrum of
Au25 (inset: the crystal structure, carbon tails are omitted for clarity). Color codes: magenta = Au core,
blue = surface Au, yellow = S. (b) Kohn−Sham orbital level diagram of Au25. Source: Adapted with permission
from [122a]. © 2008 American Chemical Society.
is well protected. In the carbon tail layer, C─H⋅⋅⋅π interactions lead to the formation of rotational
and parallel patterns of surface –R groups (Figure 1.24d).
The Au279(TBBT)84 nanocluster (where, TBBT = 4-tert-butylbenzenethiolate) was synthesized by
a LEIST method using Au333(TBBM)79 (where, TBBM = 4-tert-butylbenzyl mercaptan) as the start-
ing material, followed by reaction with excess TBBT thiol at 80 °C [108]. ESI-MS determined the
formula to be Au279(TBBT)84 (obs. MW: 68838.4 g/mol, cal.: 68836.7 g/mol), Figure 1.25a. XRC anal-
ysis (Figure 1.25b) revealed that Au279(TBBT)84 adopts a fcc structure [108], as opposed to the deca-
hedral structure of Au246(SR)80. The kernel of Au279(SR)84 is an Au147 cuboctahedron, and the next
layer is composed of 102 gold-atoms in the forms of {100} and {111} facets. The as-formed Au249 core
is then protected by 18 monomeric staples, 6 dimeric staples, and 30 simple bridging thiolates. On a
note, Dass’s group also reported this structure [109a]. Overall, Au279 is nearly spherical.
At first glance, Au246 would be thought to be metallic since its size is quite large. But, interest-
ingly, Au246 is nonmetallic (or nonplasmonic), evidenced by multiple peaks at 400, 460, and 600 nm
(a) (b) (c) (d)
Side view: Au116 {100} -S-Au-S-
Top view: Au116 {111} -S-Au-S-Au-S-&-S-
Figure 1.24 X-ray crystal structure of the 2.2 nm Au246(SR)80 nanocluster. (a) Au116 i-Dh kernel, upper panel:
side view; lower panel: top view. (b) Transition layer (colored in magenta). (c) Gold-sulfur interfacial
structure containing 20 ─S─Au─S─ staple motifs (top), 10 ─S─Au─S─Au─S─ staple motifs, and
10 ─S─ bridging motifs (bottom). (d) Surface carbon-tail layer and overall structure. Source: Reprinted with
permission from [13]. © 2016 American Association for the Advancement of Science.
(Figure 1.26a) [107]. If Au246 were metallic, it would exhibit a single SPR due to its spherical shape.
In contrast, Au279 exhibits a single peak (i.e. nascent plasmon resonance) at 506 nm
(Figure 1.26a) [108]. Similar features are also shown in transient absorption spectra by femtosec-
ond time-resolved spectroscopy (Figure 1.26b) [107, 108]. The observation of a sharp transition
(within a merely 33-atom increment) from nonmetallic Au246 to metallic Au279 is remarkable,
which sheds light on the long outstanding questions – at what size the plasmon resonance is born
and whether the transition occurs smoothly or abruptly.
Femtosecond spectroscopy further revealed that the photoexcited Au246 relaxes within ~10 ps for
the majority of the signals, but a weak, long decay component was also found, which decays to zero
in the following 200 ps [107]. Three decay components (time-constants) were found by global fit-
ting of the data (i.e. 1.9 ps, 4.6 ps, and 78 ps), with the 1.9 ps ascribed to the internal conversion
from higher to lower excited state, the 4.6 ps component to the relaxation from the lowest excited
state to the ground state, and the 78 ps to the hot ground state relaxation. The nonmetallicity of
Au246 indicates an ultrasmall band gap (not measurable but supposedly of kBT level); such a small
gap is very challenging to measure experimentally. In contrast, the electron dynamics of Au279
shows that the majority of the signals disappear within ~5 ps (the fitted lifetime τ = 1.23 ps), but the
signals do not completely decay to zero even at 100 ps, indicating an additional decay component
of long lifetime. The fast process is attributed to the electron–phonon coupling (time constant
τe–ph = 1.23 ps), and the long-lived one involves phonon–phonon coupling [108].
Further studies on the electron dynamics of Au246 and Au279 were performed under different
pump fluences (Figure 1.27). Although Au246 is large in size, it exhibits laser power-independent
dynamics (Figure 1.27a), which is similar to the features of molecules, hence, nonmetallic [107].
In contrast, the relaxation dynamics in Au279 exhibits a dependence on the laser fluence
(Figure 1.27b), indicating that Au279 has a plasma-like electronic structure, i.e. a free electron gas
is formed [108]. With the observed power dependent electron–phonon coupling in Au279, the
(a) (b)
4+
3+
2+
5000 10000 15000 20000 25000 30000 35000

m/z
Figure 1.25 (a) ESI-MS analysis of Au279(TBBT)84 (in-source ionized peaks of 4+, 3+, and 2+ sets). (b) Crystal
structure of Au279S84 by X-ray crystallography (−R groups not resolved due to insufficient crystal quality).
Yellow = S; other colors = Au. Source: Reprinted with permission from [108]. © 2018 American Chemical
Society.
intrinsic τe−ph was obtained via extrapolation to zero pump-power, which is 0.88 ps (Figure 1.27c),
comparable to the previous work on plasmonic NPs in which the τe−ph decreases as the size
becomes smaller (e.g. ~0.6 ps for ~2.2 nm Au NPs) [133]. Fitting of the Au246 data shows a decay
time constant of 4.6 ps independence of laser fluence (Figure 1.27c) [107]. Similar results on the
Au279 dynamics were obtained by Sakthivel et al. [109b]
Regarding the electronic state and optical spectral evolution of Aun(SR)m NCs, Figure 1.28 shows
a series of NCs from Au25 to Au333. Below the size of Au279, the reported NCs exhibit multiple peaks
and thus are of excitonic nature, whereas Au279 and above exhibit nascent SPRs [10, 134–136]. The
series from Au25 to Au333 implies a physical picture that the excitons in NCs larger than Au246 start
to “communicate” and develop a coherence, and the concerted excitonic transitions are generated,
manifested as a plasmon excitation in Au279 (Figure 1.28) [134]. The development of such a coher-
ence and oscillator’s energy “focusing” into the SPR energy (~2.45 eV) is intriguing (comparing the
Au246 and Au279 spectra in Figure 1.28). Beyond the Au246 to Au279 transition, Dass et al. reported
Au191 with interesting electron dynamics [135] and Higaki et al. found interesting phonon dynam-
ics in Au333 [136]. More details on large-sized NCs [137–139] remain to be revealed in future
research. For example, there is potentially some dependence on the ligand type. Wang’s group set
out to tackle alkynyl-protected Aun NCs such as Au156(CCR)60 and performed femtosecond spec-
troscopic analysis on the ultrafast electron dynamics [137]. Larger sizes are still required to be
synthesized in order to probe the nonmetal-to-metal transition in Au-alkynyl NCs. Yi et al. [139]
investigated the aqueous NCs for the nonmetal to metal transition. The shape dependence for the
transition [77] should also be investigated in future research.
Regarding the Agn NCs, work by Yang et al. [140] and Ma et al. [141] reported the crystal struc-
tures of Ag374 and Ag307, respectively, both being decahedral structures and plasmonic (single
peak at 465 nm). There seems a trend that Agn NCs give birth to the plasmon state at a much
smaller size than the Aun system, as indicated by Ag206, Ag210, and Ag211 NCs all displaying one
dominant peak at ~465 nm [142, 143], but Ag155 and smaller ones all show multiple peaks [144].
Thus, the transition seems to occur between Ag155 and Ag206 (c.f. Au246 to Au279 for the gold sys-
tem), but no detailed probing such as electron dynamics and phonon dynamics has been reported
yet on such Agn NCs.
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her at the brilliant court of the first Bourbon, where he and those of
his house struggled to maintain a reputation which had now little to
support it, but the memories of the past—and many of those were
hardly worth appealing to. He was a mere fine gentleman, bold
withal, and therewith intriguing; ever hoping that the fortunes of his
house might once more turn and bring it near a throne, and in the
meantime, making himself remarkable for his vanity, his airs of
greatness, and his affectation. Brave as he was, he left his brothers,
the cardinal and chevalier, to draw their swords and settle the
quarrels which were constantly raging on disputed questions
touching the assumed Majesty of the House of Guise.
The streets of Paris formed the stage on which these bloody
tragedies were played, but they, and all other pretensions, were
suppressed by that irresistible putter-down of such nuisances—the
Cardinal de Richelieu. He used the sword of Guise as long as it was
needed, but when Charles became troublesome the Cardinal not
only banished him, but wounded the pride of his family by placing
garrisons in the hitherto sovereign duchy of Lorraine. When Cardinal
Fleury subsequently annexed Lorraine itself to the territory of
France, the Guises thought the world was at an end. The universe,
however, survived the shock.
Duke Charles died in exile at Cune, near Sienne, in the year 1640.
Of his ten children by the Duchess de Joyeuse, he left five surviving.
He was succeeded by Henri, the eldest, who was bishop and
cardinal. He had been raised to the episcopate while yet in the arms
of his wet-nurse; and he was in frocks when on his long curls was
placed the scarlet hat of a cardinal. He was twenty years of age
when he became Duke of Guise. He at once flung away all he
possessed of his religious profession—its dress and titles, and
walked abroad, spurs on his heels, a plume in his cap, and a long
sword and a bad heart between!
The whole life of this chivalrous scoundrel was a romance, no
portion of which reflects any credit on the hero. He had scarcely
reached the age of manhood, when he entered into a contract of
marriage with the beautiful Anne of Gonzaga. He signed the
compact, not in ink, but with his own blood, calling Heaven to
witness, the while, that he would never address a vow to any other
lady. The breath of perjury had scarcely passed his lips when he
married the Countess of Bossu, and he immediately abandoned her
to sun himself in the eyes of Mademoiselle de Pons—an imperious
mistress, who squandered the property he lavished on her, and
boxed the ex-cardinal’s ears, when he attempted, with degrading
humility, to remonstrate with her for bringing down ruin upon his
estate.
He was as disloyal to his King as to his “lady;” he tampered with
rebellion, was sentenced to death, and was pardoned. But a state of
decent tranquillity agreed ill with his constitution. To keep that and
his nerves from rusting, he one day drew his sword in the street,
upon the son of Coligny, whose presence seemed a reproach to him,
and whom he slew on the spot. He wiped his bloody rapier on his
mantle, and betook himself for a season to Rome, where he
intrigued skilfully, but fruitlessly, in order to obtain the tiara for the
brother of Mazarin. Apathy would now have descended upon him,
but for a voice from the city of Naples, which made his swelling heart
beat with a violence that almost threatened to kill.
Masaniello had just concluded his brief and mad career. The
Neapolitans were not, on that account, disposed to submit again to
Spain. They were casting about for a King, when Guise presented
himself. This was in the year 1647. He left France in a frail felucca,
with a score of bold adventurers wearing the colors of Lorraine,
intertwined with “buff,” in compliment to the Duke’s mistress. The
Church blessed the enterprise. The skiff sped unharmed through
howling storms and thundering Spanish fleets; and when the Duke
stepped ashore at Naples, and mounted a charger, the shouting
populace who preceded him, burnt incense before the new-comer,
as if he had been a coming god.
For love and bravery, this Guise was unequalled. He conquered all
his foes, and made vows to all the ladies. In love he lost, however, all
the fruits of bravery. Naples was but a mock Sardanapalian court,
when the Spaniards at length mustered strongly enough to attack the
new, bold, but enervated King. They took him captive, and held him,
during four years, a prisoner in Spain. He gained liberty by a double
lie, the common coin of Guise. He promised to reveal to the Court of
Madrid the secrets of the Court of Paris; and bound himself by bond
and oath never to renew his attempt on Naples. His double knavery,
however, brought him no profit. At length, fortune seeming to
disregard the greatness of his once highly-favored house, this
restless reprobate gradually sunk into a mere court beau, passing
his time in powdering his peruke, defaming reputations, and paying
profane praise to the patched and painted ladies of the palace. He
died before old age, like most of the princes of his house: and in his
fiftieth year this childless man left his dignity and an evil name to his
nephew, Louis Joseph.
The sixth Duke bore his greatness meekly and briefly. He was a
kind-hearted gentleman, whose career of unobtrusive usefulness
was cut short by small-pox in 1671. When he died, there lay in the
next chamber an infant in the cradle. This was his little son Joseph,
not yet twelve months old, and all unconscious of his loss, in a
father; or of his gain, in a somewhat dilapidated coronet. On his
young brow that symbol of his earthly rank rested during only four
years. The little Noble then fell a victim to the disease which had
carried off his sire, and made of himself a Duke—the last, the
youngest, the most innocent, and the happiest of the race.
During a greater portion of the career of the Dukes, priest and
swordsman in the family had stood side by side, each menacing to
the throne; the one in knightly armor, the other in the dread panoply
of the Church. Of the seven ducal chieftains of the house, there is
only one who can be said to have left behind him a reputation for
harmlessness; and perhaps that was because he lived at a time
when he had not the power to be offensive. The boy on the mule, in
1506, and the child in the cradle, in 1676, are two pleasant extremes
of a line where all between is, indeed, fearfully attractive, but of that
quality also which might make not only men but angels weep.
It must be confessed that the Dukes of Guise played for a high prize;
and lost it. More than once, however, they were on the very point of
grasping the attractive but delusive prize. If they were so near
triumph, it was chiefly through the co-operation of their respective
brothers, the proud and able Cardinals. The Dukes were
representatives of brute force; the Cardinals, of that which is far
stronger, power of intellect. The former often spoiled their cause by
being demonstrative. The latter never trusted to words when silver
served their purpose equally well. When they did speak, it was with
effective brevity. We read of a Lacedemonian who was fined for
employing three words to express what might have been as
effectually stated in two. No churchman of the house of Guise ever
committed the fault of the Lacedemonian.
Cardinal John of Lorraine was the brother of the first Duke Claude.
When the latter was a boy, riding his mule into France, John was the
young Bishop-coadjutor of Metz. He was little more than two years
old when he was first appointed to this responsible office. He was a
Cardinal before he was out of his teens; and in his own person was
possessed of twelve bishoprics and archbishoprics. Of these,
however, he modestly retained but three, namely, Toul, Narbonne,
and Alby—as they alone happened to return revenues worth
acceptance. Not that he was selfish, seeing that he subsequently
applied for, and received the Archbishopric of Rheims, which he
kindly held for his nephew Charles, who was titular thereof, at the
experienced age of ten. His revenues were enormous, and he was
for ever in debt. He was one of the most skilful negotiators of his
time; but whether deputed to emperor or pope, he was seldom able
to commence his journey until he had put in pledge three or four
towns, in order to raise money to defray his expenses. His zeal for
what he understood as religion was manifested during the short but
bloody campaign against the Protestants of Alsatia, where he
accompanied his brother. At the side of the Cardinal, on the field of
battle, stood the Apostolic Commissary, and a staff of priestly aides-
de-camp. While some of these encouraged the orthodox troops to
charge the Huguenots, the principal personages kept their hands
raised to Heaven; and when the pennons of the army of Reformers
had all gone down before the double cross of Lorraine, the Cardinal
and his ecclesiastical staff rode to the church of St. Nicholas and
sang Te Deum laudamus.
The chivalrous Cardinal was another man in his residence of the
Hotel de Cluny. Of this monastery he made a mansion, in which a
Sybarite might have dwelt without complaining. It was embellished,
decorated, and furnished with a gorgeousness that had its source at
once in his blind prodigality, his taste for the arts, and his familiar
patronage of artists. The only thing not to be found in this celebrated
mansion was the example of a good life. But how could this example
be found in a prelate who assumed and executed the office of
instructing the maids of honor in their delicate duties. Do Thou says
it was an occupation for which he was pre-eminently fitted; and
Brantome pauses, in his gay illustrations of the truth of this assertion,
to remark with indignation, that if the daughters of noble houses
arrived at court, endowed with every maiden virtue, Cardinal John
was the man to despoil them of their dowry.
He was, nevertheless, not deficient in tastes and pursuits of a refined
nature. He was learned himself, and he loved learning in others. His
purse, when there was anything in it, was at the service of poor
scholars and of sages with great purposes in view. He who deemed
the slaughter of Protestant peasants a thing to thank God for, had
something like a heart for clever sneerers at Papistry and also for
Protestants of talent. Thus he pleaded the cause of the amphibious
Erasmus, extended his protection to the evangelical Clement Marot,
and laughed and drank with Rabelais, the caustic curé of Meudon.
He was, moreover, the boon companion of Francis I., a man far less
worthy of his intimacy than the equivocating Erasmus, the gentle
Marot, or roystering Rabelais, who painted the manners of the court
and church of his day, in his compound characters of Gargantua and
Panurge.
He was a liberal giver, but he gave with an ostentation for which
there is no warrant in the gospel. At one period of his life he walked
abroad with a game-bag full of crowns slung from his neck. On
passing beggars he bestowed, without counting, a rich alms,
requesting prayers in return. He was known as the “game-bag
Cardinal.” On one occasion, when giving largesse to a blind
mendicant in Rome, the latter was so astonished at the amount of
the gift, that, pointing to the giver, he exclaimed, “If thou art not
Jesus Christ, thou art John of Lorraine.”
He was bold in his gallantry. When sent by Francis I. to negotiate
some political business with the pope, he passed through Piedmont,
where he was for a while the guest of the Duke and Duchess of
Savoy. The duchess, on the cardinal being presented, gravely
offered her hand (she was a Portuguese princess) to be kissed. John
of Lorraine, however, would not stoop so low, and made for her lips.
A struggle ensued, which was maintained with rude persistance on
one side, and with haughty and offended vigor on the other, until her
highness’s head, being firmly grasped within his eminence’s arm, the
cardinal kissed the ruffled princess two or three times on the mouth,
and then, with an exultant laugh, released her.
The second cardinal of this branch, Charles of Lorraine, was brother
of the second duke. He was the greatest man of his family, and the
most powerful of his age. His ambition was to administer the
finances of France, and he did so during three reigns, with an annual
excess of expenditure over income, of two millions and a half. He
was rather dishonest than incapable. His enemies threatened to
make him account; he silenced them with the sound of the tocsin of
St. Bartholomew, and when the slaughter was over he merrily asked
for the presence of the accusers who had intended to make him
refund.
He was an accomplished hypocrite, and at heart a religious reformer.
At last he acknowledged to the leaders of the reformatory
movement, whom he admitted to his familiarity, that the Reformation
was necessary and warrantable; and yet policy made of him the
most savage enemy that Protestantism ever had in France. He
urged on the king to burn noble heretics rather than the common
people; and when Henri was touched with compassion, in his dying
moments, for some Protestant prisoners capitally condemned, the
cardinal told him that the feeling came of the devil, and that it was
better they should perish. And they perished.
He introduced the Inquisition into France, and was made Grand
Inquisitor at the moment the country was rejoicing for the recovery of
Calais from the English. And this was the man who, at the Council of
Trent, advocated the celebration of divine worship in the vernacular
tongue. He was the friend of liberty to the Gallican church, but he
took the other side on finding that liberal advocacy periled his
chances of being pope. The living pope used and abused him. “I am
scandalized,” said his holiness, “at finding you still in the enjoyment
of the revenues of so many sees.” “I would resign them all,” said the
cardinal, “for a single bishopric.” “Which bishopric?” asked the pope.
“Marry!” exclaimed Cardinal Charles, “the bishopric of Rome.”
He was as haughty as he was aspiring. The Guise had induced the
weak Anthony of Navarre to turn Romanist; but the cardinal did not
treat that king with more courtesy on that account. One frosty
morning, not only did the princely priest keep the mountain king
tarrying at his garden gate for an audience, but when he went down
to his majesty, he listened, all befurred as he was, to the shivering
monarch who humbly preferred his suit, cap in hand.
He was covetous and haughty, but he sometimes found his match.
His niece, Mary Stuart, had quarreled with Catherine de Medicis,
whose especial wrath had been excited by Mary’s phrase applied to
Catherine, of “The Florentine tradeswoman.” The Scottish Queen
resolved, after this quarrel, to repair to the North. The cardinal was at
her side when she was examining her jewels, previously to their
being packed up. He tenderly remarked that the sea was dangerous,
the jewels costly, and that his niece could not do better than leave
them in his keeping. “Good uncle,” said the vivacious Mary, “I and
my jewels travel together. If I trust one to the sea, I may the other;
and therewith, adieu!” The cardinal bit his lips and blessed her.
Ranke is puzzled where to find the principal author of the massacre
of St. Bartholomew. There is no difficulty in the matter. The Guises
had appealed to the chances of battle to overcome their chief
adversaries in the kingdom. But for every Huguenot father slain,
there arose as many filial avengers as he had sons. The causes of
quarrel were individual as well as general. A Huguenot had slain the
second Duke, and his widow was determined to be avenged. The
Cardinal was wroth with the King for retaining Protestant archers in
his body-guard. The archers took an unclean vengeance, and defiled
the pulpit in the Chapel Royal, wherefrom the Cardinal was
accustomed to denounce the doctrine of their teachers. His
Eminence formed the confederacy by which it was resolved to
destroy the enemy at a blow. To the general causes, I need not
allude. The plot itself was formed in Oliver Clisson’s house, in Paris,
known as “the Hotel of Mercy.” But the representatives of Rome and
Spain, united with those of France, met upon the frontier, and there
made the final arrangements which were followed by such terrible
consequences. When the stupendous deed was being done, the
Cardinal was absent from France; but he fairly took upon himself the
guilt, when he conferred the hand of his illegitimate daughter Anne
d’Arne on the officer Besme whose dagger had given the first mortal
stab to Coligny, the chief of the immolated victims of that dreadful
day—and Rome approved.
As a public controversialist he shone in his dispute with Beza. Of his
pride, we have an illustration in what is recorded of him in the
Council of Trent. The Spanish embassador had taken a place, at
mass, above that of the embassador from France. Thereupon, the
reverend Cardinal raised such a commotion in the cathedral, and
dwelt so loudly and strongly in expletives, that divine worship was
suspended, and the congregation broke up in most admired disorder.
So at the coronation, in the Abbey of St. Dennis, of the Queen of
Charles IX. The poor, frail, Austrian Princess Elizabeth, after being
for hours on her knees, declared her incapacity for remaining any
longer without some material support from food or wine. The
Cardinal declared that such an irreligious innovation was not to be
thought of. He stoutly opposed, well-fed man that he was, the
supplying of any refreshment to the sinking Queen; and it was only
when he reflected that her life might be imperiled that he consented
to “the smallest quantity of something very light,” being administered
to her.
He was the only man of his family who was not possessed of the
knightly virtue of bravery. He was greatly afraid of being
assassinated. In council, he was uncourteous. Thus, he once
accused the famous Chancellor le Hospital of wishing to be “the cock
of the assembly,” and when the grave chancellor protested against
such language, the Cardinal qualified him as “an old ram.” It may be
added that, if he feared the dagger directed by private vengeance,
he believed himself protected by the guardianship of Heaven, which
more than once, as he averred, carried him off in clouds and
thunder, when assassins were seeking him. He was wily enough to
have said this, in order to deter all attempts at violence directed
against himself.
He died edifyingly, kissed Catherine de Medicis, and was believed by
the latter, to mysteriously haunt her, long after his death. The real
footing on which these two personages stood has yet to be
discovered by curious inquiries.
The Cardinal-brother of the third Duke, Louis of Lorraine, loved good
living, and was enabled at an early age to indulge his propensities,
out of the rich revenues which he derived from his numerous
ecclesiastical preferments. He held half a dozen abbeys while he
was yet in his cradle; and he was a bishop at the mature age of
eighteen. Just before his death, in 1598, when he was about fifty
years of age, he resigned his magnificent church appointments, in
favor of his nephew and namesake, who was to be a future Cardinal
at the side of the fourth Duke. Louis was a man of ability and of wit.
He chose a device for his own shield of arms. It consisted of nine
zeros, with this apt motto: “Hoc per se nihil est; sed si minimum
addideris, maximum erit,” intending, it is said, to imply that man was
nothing till grace was given him. He was kindly-dispositioned, loved
his ease, was proud of his church, and had a passion for the bottle.
That was his religion. His private life was not marked by worse traits
than those that characterized his kinsmen in the priesthood. He
showed his affection for his mother after a truly filial fashion,
bequeathing to her all his estates, in trust, to pay his debts.
The third duke had a second cardinal-brother, known as the Cardinal
de Guise, who was murdered by Henri III. He was an intriguer; but
as brave as any knight of his family. It was long before the king could
find men willing to strike a priest; and when they were found, they
approached him again and again, before they could summon nerve
wherewith to smite him. After all, this second murder at Blois was
effected by stratagem. The cardinal was requested to accompany a
messenger to the royal presence. He complied with some misgiving,
but when he found himself in a dark corridor with four frowning
soldiers, he understood his doom; requested a few moments respite
to collect his thoughts; and then, enveloping his head in his outer
robe, bade them execute their bloody commission. He was instantly
slain, without offering resistance, or uttering a word.
This cardinal was father of five illegitimate sons, of whom the most
celebrated was the Baron of Ancerville, or, as he proudly designated
himself, “Bastard of Guise.”
By the side of the son of Balafré, Charles, the fourth duke, there
stood the last cardinal-brother who was able to serve his house, and
whose character presents any circumstance of note. This cardinal, if
he loved anything more than the bottle, was fondest of a battle. He
characteristically lost his life by both. He was present at the siege of
St. Jean d’Angely, held by the Protestants in the year 1621. It was on
the 20th of May; and the sun was shining with a power not known to
our severe springs. The cardinal fought like a fiend, and swore with
more than fiendish capacity. The time was high noon, and he himself
was in the noontide of his wondrous vigor, some thirty years of age.
He was laying about him in the bloody mêlée which occurred in the
suburb, when he paused for awhile, panting for breath and streaming
with perspiration. He called for a flask of red wine, which he had
scarcely quaffed when he was seized with raging fever, which
carried him off within a fortnight. He was so much more addicted to
knightly than to priestly pursuits, that, at the time of his death, a
negotiation was being carried on to procure from the pope
permission for the cardinal to give up to his lay-brother, the Duc de
Chevreuse, all his benefices, and to receive in return the duke’s
governorship of Auvergne. He was for ever in the saddle, and never
more happy than when he saw another before him with a resolute
foe firmly seated therein. He lived the life of a soldier of fortune, or
knight-errant; and when peace temporarily reigned, he rode over the
country with a band of followers, in search of adventures, and always
found them at the point of their swords. He left the altar to draw on
his boots, gird his sword to his hip, and provoke his cousin De
Nevers to a duel, by striking him in the face. The indignant young
noble regretted that the profession of his insulter covered the latter
with impunity, and recommended him, at the same time, to abandon
it, and to give De Nevers satisfaction. “To the devil I have sent it
already!” said the exemplary cardinal, “when I flung off my frock, and
belted on my sword:” and the two kinsmen would have had their
weapons in each other’s throat, but for the royal officers, who
checked their Christian amusement.
This roystering cardinal, who was interred with more pomp than if he
had been a great saint, or a merely honest man, left five children.
Their mother was Charlotte des Escar. They were recognised as
legitimate, on allegation that their parents had been duly married, on
papal dispensation. He was the last of the cardinals, and was as
good a soldier as any of the knights.
Neither the pride nor the pretensions of the house expired with either
Dukes or Cardinals. There were members of the family whose
arrogance was all the greater because they were not of the direct
line of succession. Their great ambition in little things was satisfied
with the privilege granted to the ladies of Guise, namely, the one
which they held in common with royal princesses, at being presented
at court previous to their marriage. This ambition gained for them,
however, the hatred of the nobles and the princes of the Church, and
at length caused a miniature insurrection in the palace at Versailles.
The occasion was the grand ball given in honor of the nuptials of
Marie Antoinette and the Dauphin. Louis XV. had announced that he
would open the brilliant scene by dancing a minuet with Mlle. de
Lorraine, sister of the Prince de Lambesc. The uproar that ensued
was terrific. The entire body of nobility protested against such
marked precedence being allowed to the lady in question. The
Archbishop of Rheims placed himself at the head of the opposing
movement; and, assembling the indignant peerage, this successor of
the Apostles, in company with his episcopal brother from Noyon,
came to the solemnly important resolution, that between the princes
of the blood-royal and haute noblesse there could be no intermediate
rank; and that Mlle. de Lorraine, consequently, could not take
precedence of the female members of the aristocracy, who had been
presented. A memorial was drawn up. The entire nobility, old and
new, signed it eagerly; and the King was informed that if he did not
rescind his determination, no lady would dance at the ball after the
minuet in question had been performed. The King exerted himself to
overcome the opposition: but neither bishops nor baronesses would
give way. The latter, on the evening of the ball, walked about the
grand apartments in undress, expressed loudly their resolution not to
dance, and received archiepiscopal benison for their pious obstinacy.
The matter was finally arranged by compromise, whereby the
Dauphin and the Count d’Artois were to select partners among the
nobility, and not, as was de rigueur, according to the law of minuets,
among princesses of their own rank. The hour for opening the
famous ball was retarded in order to give the female insurrectionists
time to dress, and ultimately all went off à merveille!
With the Prince de Lambesc above-named, the race of Guise
disappeared altogether from the soil of France. He was colonel of
the cavalry regiment, Royal Allemand, which in 1789 came into
collision with the people. The Prince was engaged, with his men, in
dispersing a seditious mob. He struck one of the most conspicuous
of the rioters with the flat of his sword. This blow, dealt by a Guise,
was the first given in the great Revolution, and it helped to deprive
Louis XVI. of his crown. The Prince de Lambesc was compelled to
fly from the country, to escape the indignation of the people. Nearly
three centuries before, his great ancestor, the boy of the mule, had
entered the kingdom, and founded a family which increased in
numbers and power against the throne, and against civil and
religious liberty. And now, the sole survivor of the many who had
sprung from this branch of Lorraine, as proud, too, as the greatest of
his house, having raised his finger against the freedom of the mob,
was driven into exile, to seek refuge for a time, and a grave for age,
on the banks of the distant Danube.
When Cardinal Fleury annexed the Duchy of Lorraine to France, it
was by arrangement with Austria; according to which, Francis, Duke
of Lorraine, received in exchange for his Duchy, the Grand Duchy of
Tuscany and the hand of Maria Theresa. Their heirs form the
imperial house of Hapsburgh-Lorraine. Such of my readers as have
visited Nancy, the capital of old Lorraine, will remember there the
round chapel near what is left of the old palace of the old Dukes.
This chapel contains the tombs of the principal of the twenty-nine
Dukes who ruled sovereignly in Lorraine. The expense of supporting
the service and fabric, altar and priests, connected with this chapel,
is sustained entirely by Austria. It is the only remnant preserved of
the Lorraine sovereignty of the olden time. The priests and employes
in the edifice speak of Hapsburgh-Lorraine as their house, to which
they owe exclusive homage. When I heard expression given to this
sentiment, I was standing in front of the tomb of that famous etcher,
old Jean Callot. The latter was a native of Nancy; and I could almost
fancy that his merry-looking lip curled with scorn at the display of this
rag of pride in behalf of the house of Lorraine.
With the story of part of that house I fear I may have detained the
reader too long. I will tell more briefly the shifting fortunes of a
material house, the knightly edifice of Rambouillet.
THE RECORD OF RAMBOUILLET.
“Imagine that this castle were your court,
And that you lay, for pleasure, here a space,
Not of compulsion or necessity.”— Kit Marlowe.
Rambouillet is an old château where feudal knights once lived

like little kings. In its gardens Euphuism reigned supreme. It is a
palace, in whose chambers monarchs have feasted, and at whose
gates they have asked, when fugitives, for water and a crust of
bread. It commenced its career as a cradle of knights; it is finishing it
as an asylum for the orphan children of warriors. The
commencement and finale are not unworthy of one another; but,
between the two, there have been some less appropriate disposals
of this old chevalier’s residence. For a short period it was something
between Hampton Court and Rosherville. In the very place where
the canons of the Sainte Chapelle were privileged to kiss the cheeks
of the Duchess of Burgundy, the denizens of the Faubourg St.
Antoine could revel, if they could only pay for their sport. Where the
knightly D’Amaurys held their feudal state, where King Francis
followed the chase, and the Chevalier Florian sang, and Penthièvre
earned immortality by the practice of heavenly virtues; where Louis
enthroned Du Barry, and Napoleon presided over councils, holding
the destiny of thrones in the balance of his will, there the sorriest
mechanic had, with a few francs in his hand, the right of entrance.
The gayest lorettes of the capital smoked their cigarettes where Julie
D’Angennes fenced with love; and the bower of queens and the
refuge of an empress rang with echoes, born of light-heartedness
and lighter wine. Louis Napoleon has, however, established a better
order of things.
To a Norman chief, of knightly character, if not of knightly title, and to
the Norman tongue, Rabouillet, as it used to be written, or the
“Rabbit warren,” owes the name given to the palace, about thirteen
leagues from Paris, and to the village which clusters around it. The
former is now a quaint and confused pile, the chief tower of which
alone is now older than the days of Hugues Capet. Some authors
describe the range of buildings as taking the form of a horseshoe;
but the hoof would be indescribable to which a shoe so shaped could
be fittingly applied. The changes and additions have been as much
without end as without taste. In its present architectural entirety it
wears as motley an aspect as Cœur de Lion might, were he to walk-
down Pall Mall with a modern paletót over his suit of complete steel.
The early masters of Rambouillet were a knightly, powerful but
uninteresting race. It is sufficient to record of the chivalric D’Amaurys
that they held it, to the satisfaction of few people but themselves,
from 1003 to 1317. Further record these sainted proprietors require
not. We will let them sleep on undisturbedly, their arms crossed on
their breast, in the peace of a well-merited oblivion. Requiescat!
One relic of the knightly days, however, survived to the period of the
first French Revolution. In the domain of Rambouillet was the fief of
Montorgueil. It was held by the prior of St. Thomas d’Epernon, on the
following service: the good prior was bound to present himself yearly
at the gate of Rambouillet, bareheaded, with a garland on his brow,
and mounted on a piebald horse, touching whom it was bad service
if the animal had not four white feet.
The prior, fully armed like a knight, save that his white gloves were of
a delicate texture, carried a flask of wine at his saddle-bow. In one
hand he held a cake, to the making of which had gone a bushel of
flour—an equal measure of wheat was also the fee of the lord. The
officers of the latter examined narrowly into the completeness of the
service. If they pronounced it imperfect the prior of Epernon was
mulcted of the revenues of his fief for the year ensuing.
In later days the ceremony lost much of its meaning; but down to the
period of its extinction, the wine, the cake, and the garland, were
never wanting; and the maidens of Rambouillet were said to be more
exacting than the baronial knights themselves, from whom many of
them were descended. The festival was ever a joyous one, as
became a feudal lord, whose kitchen fireplace was of such
dimensions that a horseman might ride into it, and skim the pot as he
stood in his stirrups.
It is a singular thing that scarcely a monarch has had anything to do
with the knightly residence of Rambouillet, but mischance has
befallen him. The kings were unjust to the knights, and the latter
found for the former a Nemesis. Francis I. was hunting in the woods
of Rambouillet when he received the news of the death of Henry VIII.
that knight-sovereign, with whom he had struggled on the Field of
the Cloth of Gold. With the news, he received a shock, which the
decay sprung from various excesses could not resist. He entered the
chateau as the guest of the Chevalier d’Angennes, in whose family
the proprietorship then resided. The chamber is still shown wherein
he died, roaring in agony, and leaving proof of its power over him, in
the pillow, which, in mingled rage and pain, he tore into strips with
his teeth.
The French author, Leon Gozlau, has given a full account of the
extraordinary ceremonies which took place in honor of Francis after
his death. In front of the bed on which lay the body of the king, says
M. Gozlau, “was erected an altar covered with embroidered cloth; on
this stood two gold candlesticks, bearing two lights from candles of
the whitest wax. The cardinals, prelates, knights, gentlemen, and
officers, whose duty it was to keep watch, were stationed around the
catafalque, seated on chairs of cloth of gold. During the eleven days
that the ceremony lasted, the strictest etiquette of service was
observed about the king, as if he had been a living monarch in
presence of his court. His table was regularly laid out for dinner, by
the side of his bed. A cardinal blessed the food. A gentleman in
waiting presented the ewer to the figure of the dead king. A knight
offered him the cup mantling with wine: and another wiped his lips
and fingers. These functions, with many others, took place by the
solemn and subdued light of the funeral torches.”
The after ceremonies were quite as curious and extraordinarily
magnificent; but it is unnecessary to rest upon them. A king, in not
much better circumstances than Francis, just before his death, slept
in the castle for one night in the year 1588. It was a night in May, and
the knight proprietor Jean d’Angennes, was celebrating the marriage
of his daughter. The ceremony was interrupted by a loud knocking at
the castle gates. The wary Jean looked first at the clamorous visitors
through the wicket, whence he descried Henri III. flurried, yet
laughing, seated in an old carriage, around which mustered dusty
horsemen, grave cavaliers, and courtiers scantily attired. Some had
their points untrussed, and many a knight was without his boots. An
illustrious company, in fact; but there were not two nobles in their
united purses. Jean threw open his portals to a king and his knights
flying from De Guise. The latter had got possession of Paris, and
Henri and his friends had escaped in order to establish the regal
authority at Chartres. The two great adversaries met at Blois: and
after the assassination of Guise, the king, with his knights and
courtiers, gallopped gayly past Rambouillet on his return to Paris, to
profit by his own wickedness, and the folly of his trusty and well-
beloved cousin, the duke.
Not long before this murder was committed, in 1588, the Hotel Pisani
in Paris was made jubilant by the birth of that Catherine de
Vivonnes, who was at once both lovely and learned. She lived to
found that school of lingual purists whose doings are so pleasantly
caricatured in the Précieuses Ridicules of Molière. Catherine
espoused that noble chevalier, Charles d’Angennes, Lord of
Rambouillet, who was made a marquis for her sake. The chevalier’s
lady looked upon marriage rather as a closing act of life than
otherwise; but then hers had been a busy youth. In her second lustre
she knew as many languages as a lustrum has years. Ere her fourth
had expired, her refined spirit and her active intellect were disgusted
and weary with the continual sameness and the golden emptiness of
the court. She cared little to render homage to a most Christian king
who disregarded the precepts of Christianity; or to be sullied by
homage from a monarch, which could not be rendered without insult
to a virtuous woman. Young Catherine preferred, in the summer eve,
to lie under the shadow of her father’s trees, which once reared a
world of leafy splendor on the spot now occupied by the Palais
Royal. There she read works coined by great minds. During the long
winter evenings she lay in stately ceremony upon her bed, an
unseemly custom of the period, and there, surrounded by chevaliers,
wits, and philosophers, enjoyed and encouraged the “cudgelling of
brains.” At her suggestion the old hotel was destroyed, and after her
designs a new one built; and when, in place of the old dark panelling,
obscurely seen by casements that kept out the light, she covered the
walls of her reception-rooms with sky-blue velvet, and welcomed the
sun to shine upon them, universal France admiringly pronounced her
mad, incontinently caught the infection, and broke out into an
incurable disease of fancy and good taste.
The fruit of the union above spoken of was abundant, but the very
jewel in that crown of children, the goodliest arrow in the family
quiver, was that Julie d’Angennes who shattered the hearts of all the
amorous chevaliers of France, and whose fame has, perhaps,
eclipsed that of her mother. Her childhood was passed at the feet of
the most eminent men in France; not merely aristocratic knights, but
as eminent wits and philosophers. By the side of her cradle, Balzac
enunciated his polished periods, and Marot his tuneful rhymes,
Voiture his conceits, and Vaugelas his learning. She lay in the arms
of Armand Duplessis, then almost as innocent as the little angel who
unconsciously smiled on that future ruthless Cardinal de Richelieu;
and her young ear heard the elevated measure of Corneille’s
“Melite.” To enumerate the circles which was wont to assemble
within the Hôtel Rambouillet in Paris, or to loiter in the gardens and
hills of the country château, whose history I am sketching, would
occupy more space than can be devoted to such purpose. The circle
comprised parties who were hitherto respectively exclusive. Knights
met citizen wits, to the great edification of the former; and
Rambouillet afforded an asylum to the persecuted of all parties. They
who resisted Henry IV. found refuge within its hospitable walls, and
many nobles and chevaliers who survived the bloody oppression of
Richelieu, sought therein solace, and balm for their lacerated souls.
Above all, Madame de Rambouillet effected the social congregation
of the two sexes. Women were brought to encounter male wits,
sometimes to conquer, always to improve them. The title to enter
was, worth joined with ability. The etiquette was pedantically strict,
as may be imagined by the case of Voiture, who, on one occasion,
after conducting Julie through a suite of rooms, kissed her hand on
parting from her, and was very near being expelled for ever from
Rambouillet, as the reward of his temerity. Voiture subsequently
went to Africa. On his return, he was not admitted to the illustrious
circle, but on condition that he narrated his adventures, and to these
the delighted assembly listened, all attired as gods and goddesses,
and gravely addressing each other as such. Madame de Rambouillet
presided over all as Diana, and the company did her abundant
homage. This, it is true, was for the nonce; but there was a
permanent travesty notwithstanding. It was the weak point of this
assembly that not only was every member of it called by a feigned,
generally a Greek, name, but the same rule was applied to most
men and things beyond it; nay, the very oaths, for there were little
expletives occasionally fired off in ecstatic moments, were all by the
heathen gods. Thus, as a sample, France was Greece. Paris was
Athens; and the Place Royale was only known at Rambouillet as the
Place Dorique. The name of Madame de Rambouillet was
Arthemise; that of Mademoiselle de Scudery was Aganippe; and
Thessalonica was the purified cognomen of the Duchess de
Tremouille. But out of such childishness resulted great good,
notwithstanding that Molière laughed, and that the Academie derided
Corneille and all others of the innovating coterie. The times were
coarse; things, whatever they might be, were called by their names;
ears polite experienced offence, and at Rambouillet periphrasis was
called upon to express what the language otherwise conveyed
offensively by the medium of a single word. The idea was good,
although it was abused. Of its quality some conjecture may be
formed by one or two brief examples; and I may add, by the way,
that the French Academy ended by adopting many of the terms
which it at first refused to acknowledge. Popularity had been given to
much of the remainder, and thus a great portion of the vocabulary of
Rambouillet has become idiomatic French. “Modeste,” “friponne,”
and “secrète,” were names given to the under-garments of ladies,
which we now should not be afraid to specify. The sun was the
“amiable illuminator;” to “fulfil the desire which the chair had to
embrace you,” was simply to “sit down.” Horses were “plushed
coursers;” a carriage was “four cornices,” and chairmen were
“baptized mules.” A bed was the “old dreamer;” a hat, the “buckler
against weather;” to laugh was to “lose your gravity;” dinner was the
“meridional necessity;” the ear was the “organ, or the gate of
hearing;” and the “throne of modesty” was the polished phrase for a
fair young cheek. There is nothing very edifying in all this, it is true;
but the fashion set people thinking, and good ensued. Old
indelicacies disappeared, and the general, spoken language was
refined. If any greater mental purity ensued from the change, I can
scarcely give the credit of it to the party at Rambouillet, for, with all
their proclaimed refinement, their nicety was of the kind described in
the well-known maxim of the Dean of St. Patrick.
One of the most remarkable men in the circle of Rambouillet, was
the Marquis de Salles, Knight of St. Louis. He was the second son of
the Duke de Montausier, and subsequently inherited the title. At the
period of his father’s death, his mother found herself with little dower
but her title. She exerted herself, however, courageously. She
instructed her children herself, brought them up in strict Huguenot
principles, and afterward sent them to the Calvinistic college at
Sedan, where the young students were famous for the arguments
which they maintained against all comers—and they were many—
who sought to convert them to popery. At an early age he acquired
the profession of arms, the only vocation for a young and portionless
noble; and he shed his blood liberally for a king who had no thanks
to offer to a protestant. His wit, refinement, and gallant bearing,
made him a welcome guest at Rambouillet, where his famous
attachment to Julie, who was three years his senior, gave matter for
conversation to the whole of France. Courageous himself, he loved
courage in others, and his love for Julie d’Angennes, was fired by the
rare bravery exhibited by her in tending a dying brother, the
infectious nature of whose disorder had made even his hired nurses
desert him. In the season of mourning, the whole court, led by
royalty, went and did homage to this pearl of sisters. But no
admiration fell so sweetly upon her ear as that whispered to her by
the young Montausier. One evidence of his chivalrous gallantry is yet
extant. It is in that renowned volume called the “Guirlande de Julie,”
of which he was the projector, and in the accomplishing of which,
knights, artists, and poets, lent their willing aid. It is superb vellum
tome. The frontispiece is the garland or wreath, from which the
volume takes its name. Each subsequent page presents one single

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Atomically Precise Nanochemistry 1st

Edition Rongchao Jin

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Library of Congress Cataloging-in-Publication Data

Set in 9.5/12.5pt STIXTwoText by Straive, Pondicherry, India

List of Contributors xiii

1 Introduction to Atomically Precise Nanochemistry 1

2 Total Synthesis of Thiolate-Protected Noble Metal Nanoclusters 57

3 Thiolated Gold Nanoclusters with Well-Defined Compositions and Structures 87

3.4.2.2 Biological Labeling and Biomedicine 127

4 Structural Design of Thiolate-Protected Gold Nanoclusters 141

5 Electrocatalysis on Atomically Precise Metal Nanoclusters 161

5.5 Conclusions and Outlook 187

6 Atomically Precise Metal Nanoclusters as Electrocatalysts: From Experiment

7 Ag Nanoclusters: Synthesis, Structure, and Properties 227

8 Atomically Precise Copper Nanoclusters: Syntheses, Structures, and Properties 257

10 Atomically Precise Heterometallic Rhodium Nanoclusters Stabilized by Carbonyl

10.2 Synthesis of Heterometallic Rhodium Carbonyl Nanoclusters 311

12 On-Surface Synthesis of Polyacenes and Narrow Band-Gap Graphene Nanoribbons 373

12.2 Bottom-Up Synthesis of Graphene Nanoribbons 375

13 A Branch of Zintl Chemistry: Metal Clusters of Group 15 Elements 395

14 Exploration of Controllable Synthesis and Structural Diversity of Titanium─Oxo

15 Atom-Precise Cluster-Assembled Materials: Requirement and Progresses 453

16 Coinage Metal Cluster-Assembled Materials 479

Osman M. Bakr Ning Chen

Cristiana Cesari Cristina Femoni

Mei-Yan Gao Rongchao Jin

Wenhua Han Sukhendu Mandal

De-en Jiang Jiawei Qiu

Hoeun Seong Xin Xia

Yang-Rong Yao Lei Zhang

Peng Yuan Lihao Zheng

Stefano Zacchini Manman Zhou

Rongchao Jin and De-en Jiang

Introduction to Atomically Precise Nanochemistry

1.1 Why Atomically Precise Nanochemistry?

1.1.1 Motivations from Nanoscience Research

Gas phase Nanoscience

Inorganic chemistry Supramolecular

3000 6000 9000 12000 15000 18000

(a) (b) (c)

1.1.2 Motivations from Inorganic Chemistry Research

1.1.3 Motivations from Gas Phase Cluster Research

1.1.4 Motivations from Other Areas

Au+4 Au+5 Au+6 Au+7 Au+8

Au+9 Au+10 Au+11 Au+12 Au+13

1.2 Types of Nanoclusters Covered in This Book

...... Au25 Au38 Au144 Au246 Au279 Au333 ......

1.0 nm 1.2 nm 1.7 nm 2.2 nm 2.2 nm 2.3 nm

1.2.2 Endohedral Fullerenes and Graphene Nanoribbons

1.2.3 Zintl Clusters

C60 cage La2@lh(7)–C80 Gd3N@C2(22010)–C78 Sc3CN@lh(7)–C80

[As@Ni12@As20]3– [Sb3Au3Sb3]3– [Co@Sn6Sb6]3–

1.2.4 Metal-Oxo Nanoclusters

Ti16 ring Ti32 ring

Ti42 spherical cage Ti52 dense structure

1.3 Some Fundamental Aspects

1.3.1 Synthesis and Crystallization

Figure 1.11 Size-focusing synthesis of 10k 24k 31k 56k 71k

10000 15000 20000 25000 30000

X-ray crystallography (single crystal X-ray diffraction)

Atomic resolution (<1 Å)

1.3.2 Structural and Bonding Patterns