CTs FANTPPATUULTVL> BN OO ey elt) NY SATNIFION SINVOYO 40 AULSINAHIOLOHd LTE MTOR Lele) | MODERN MOLECULAR PHOTOCHEMISTRYFora crystal-clearintroduction to organic photochemistry in pictorial ang intuttive terms, this eee eu ecu me Ream Mom DT aa ee ee ee MEU MUS A ne eeu oie core ue aCe uue mete eee ts simple paradigms that can be applied to all organic functional groups. The critical concepts of electronic and spin interactions are presented in pictorial terms that can be readily Me Lec tieer Ceueet elt Se Cee aU Rn em Nicholas J, Turro is the Wiliam P. Schweitzer Professor of Chemist at Columbia University. He has been widely recognized by nation and intemational awards as a leader and pioneer in the area o Gee meu Oe Meal nau ego A fret mea Eee (eee onto eee cece V. Ramamurthy (Murthy) is currently Professor and Chair of Chemistry Pe eeu see eae Institute of Science, Bangalore, The Du Pont Company and Tul University. He is well-known for his contributions in the area of solid- Beer mene et en ecu pacer un S31NDF1OW JINVONO 40 MoM) MSSe TELM GSM ur OP LET MS cece eM Opel an me) Photochemistry at the University of Ottawa. He is widely recognized Tee eno SMSO LS me ue Tee Mee chemistry. His current research interests include the apf ero e cue eu Were se eee meal] Reon ey Romie Es Patel RootDEDALUS - Acervo - FFCLRP. Modern Molecular = Photochemistry of Organic Molecules Nicholas J. Turro 20800042172University Science Books swmeuscbookscom ‘To my one and only Muse and Sout Mate Sandy, ‘Tomy wo Foxes, Cindy and Cl ]onucrion wana Fal Angsty, Wi Stine ‘Tomy five Munchkins, Nicholas, C DESIGN rol C, Anagnostopoulos tuusteatons Laurel Molle, ohn Choi, LineWouks PROOFREADERS Rick Camp, Yenie Oeron comeostron Wiel Softwar, wing 215% ‘covER neston Genet loko MCiew ancree & winse -Maplo-Vil Book Manufsctrng Groop lie, Catherine, Maria, and Julia, wr ‘Tomy Jyothi: Jayalakshni, Rajec, and Pradeep. VR “This books printed on ac fe pape ‘Tomy wife Bd, Copyright © 2010 by University Science Books For 40 years of love, friendship, and patience, ICS. Reproduction o taslton of ny partf this work beyond thst permite by Section 107 os 108 uf the 1976 Usited States Copyright Act witht the permsin ofthe copyright owner is laf Requests for perissionor fuer information hobld be reseed ote Penmisins Deartnet, University Science Books. L ‘Turo, Nicklas, 1938 ‘Modem meleclar phoochemsty of one molecules Nebo J Taro, {Remar ean Sesiano. Ben Includes bibtiograhicl references and ind, ISDN 978-1-891389.25-2 (a. pape 1. Organic photochemistry. 2. Organic empouns. 1. Ramamurthy, ¥. .Seaiano, J.C. Guan), 1943 I Tite sy OF Conntss CATALOGING: PumLicATION Data apart? 20 Sirs ne anon, ce RC Pit nee Sse Ameen fon OR woe 7654321 | Aol aed ofBrief Contents Prolace xx CHAPTER 1 Molocular Photochemistry of Organic Compounds: ‘An Overview 1 ‘CHAPTER2 Electronic, Vibrational, and Spin Configurations of Electronically Excited States 39 CHAPTERS Tiansitions between States: Photophysical Processes 109 CHAPTER 4 Radiative Transitions between Electronic Stalas 169 CHAPTERS. Photophysical Hadialiontess Transitions 265 CHAPTER 6 A Theory of Molecular Organic Photochemistry 319 CHAPTER 7 Energy Transfer and Electron Transfer 383 CHAPTER 8 Mechanistic Organic Photochemistry 483, CHAPTER 9 Photochemistry of Carbonyl Compounds 623 ‘CHAPTER 10. Photochemistry of Olelins 705 HAPTER TI Pholochemisty of Enones and Dienones aot hapten 12 Pholochemisty of Aromatic Molecules 847 CHaPTER 13. Supramolecular Organic Photochemistry: The Control of Organic Photochemistry and Photophysics through Intermolecular interactions 925 CHAPTER 14 Molecular Oxygen and Organie Photochemistry 1001 CHAPTER 15 A Generalization ofthe Photochemistry of Organic Molecules 1043 Index 1055HAPTER 1 1 12 1s 14 Ls 16 7 18 19 110 Lu 12 113 Ld Contents Proface xxi Molecular Photochemistry of Organic Compounds: An Overviow ‘What Is Molecular Organie Photochomistry? 1 Leaming Molecular Organic Photochemistry through the Visualization of Molecular Structures and the Dynamics of Theit ‘Transformations 3 ‘Why Study Motecutar Organic Photochemistry? 3 ‘The Value of Pictorial Representations and Visualization of Scientific Concepts 5 Scientific Paradigms of Molecular Organic Photochemistry 6 Exemplars as Guides tothe Experimental Study and Understanding ‘of Molecular Organic Photochemistry 7 ‘The Paradigm of Molecular Organic Photochemistry & PParadignis as Guides for Proceeding from the Possible tothe Plausible tothe Probable Photochemical Processes. & Some Important Questions that Will Be Answered by the Paradigms ‘of Molecular Organic Photochemistry 10 From a Global Paradigm to the Everyday Working Paradigay 11 Singlet States, Triplet States, Diradicals, and Zwiterions: Key Structures Along a Photochemical Pathway fom *R toP Ld ‘State Energy Diagrams: ‘An Energy Surface Description of Molecular Photochemistry 20 Stnucture, Bnergy, and Time: Molecttar-Level Benchmacks and Calibration Points of Photochemical Processes 25 tronic nd Spin Isomers. 16Contents 116 17 Las 19 120 cHapren2 2a 22 23 24 25 26 27 28 29 2.10 243 24 Electionically Excited St Calibration Points and Numesieal Benchmarks for Molecular Energetics 26 Counting Photons 28 ‘Computing the Fnergy of a Mole of Photons for Light of Wavelength and Frequency 29 ‘The Range of Photon Energies inthe Flectromagaetic Spectrum 29 Calibration Points and Numerical Benchmarks for Molecular Dimensions and Time Seales 33, Plan ofthe Text 35 References 38 Electconic, Vibrational, and Spin Configurations of 5 39 Visualization of the Electronically Excited Steuctures through the Paradigms of Molecular Organic Photochemistry 39 Molecular Wave Functions and Molecular Structure 42 ‘The Bom-Oppenheimer Approximation: A Stacting Point for Approximate Molecular Wave Functions and Energies 45 Important Qualitative Characteristics of Approximate Wave Functions 7 rom Postulates of Quantum Mechanics to Observations of Molecular ‘Structare: Expectation Values and Matrix Elements 49 ‘The Spirit ofthe Use of Quantum Mechanical Wave Functions, Operators, and Mateix Blements 50 From Atomic Orbital, to Molecular Orbitals ‘Configurations, to Blectonic Stas St Ground and Excited Electronic Configurations 52 ‘The Construction of Electronic States from Electronic Configurations 56 Construction of Excited Singlet and Triplet States from Electronically Excited Configurations and the Pauli Principle 56 Characteristic Configurations of Singlet and Tkiplt States: A Shorthand Notation 57 [Blectoonic Energy Difference between Molecular Singlet and Triplet States of *R: Electron Correlation and the Electron Exchange Energy 58 Evaluation of the Relative Singlet and Triplet Energies and Singlet ‘Triplet Energy Gaps for Plectronically Excited States 'R) of the Same Electronic Configuration 60 Exemplars for the Singlet ‘Triplet Split Systems 63 (@ Blectronie 25 216 au 2.8 29 220 221 222 223 224 2.25 2.26 22 2.28 229 2.30 23 233 234 235 2.36 Contents Electoonie Energy Difference between Singlet and Triplet States of Diradical Reactive Intermediates: Radical Pairs, (RP), and Biradicals, KBR) 66 ‘A Mode for Vibrational Wave Functions: The Classial Harmonie Oscillator 69 ‘The Quantum Mechanical Version of the Classical Harmonic Oscillator 75 ‘The Vibrational Levels of a Quantum Mechanical Harmonic Oscillator 77 ‘The Vibrational Wave Functions for & Quantum Mechanical Harmonic Oscillator: Visualization of the Wave Funetions for itomic Molecules 78 {A First-Order Approximation ofthe Harmonic-Oscillator Model: ‘The Anharmonic Oscillator 80 Important Properties of Vectors 85, Yector Representation of Electron Spin 86 ‘Spin Muipic Vector Model of Two Coupled Electron Spins: Singlet and Triplet States 89 ‘The Uncertainty Prine! lectwon Spin 92 Cones of Possible Orientations for Two Coupled 1/2 Spins ‘Singlet andTiplet Cones of Orientation asa Basis for Visualizing the Interconversion of Spin States 93 ‘Making Connection between Spin Angular Momentum and Magnetic Moments Due to Spin Angulae Momentum 94 ‘The Connection between Angular Momentum and Magnetic ‘Moments: A Physical Model for an Blectron with Angular Momentum 94 ‘The Magnetic Moment of an Blecton in a Bobr Orbit 95 The Connection between Magnetic Moment and Electron Spin 97 s: Allowed Orientations of Electron Spins 87 le and Cones of Possible Orientations for ‘Magnetic Energy Levels in an Applied Magnetic Field for a Classical Magnet 99 ‘Quantum Magnets in the Absence of Coupling Magnetic Fields 101 Quantum Mechanical Magnets in a Magnetic Field: Consteuting a Magnetic State Energy Diagram for Spins in an Applied Magnetic Field 102 ‘Magnetic Energy Diagram fora Single Electron Spin andl for Two Coupled Bleetron Spins 103,Contents 238 239 240 cnarren 3 3 32. 33 34 35 36 31 38 39 3.10 3 32 3.13 a4 aus 316 39 38 3.19 320 ‘Magnetic Energy Diagrams Including the Electton Exchange Interaction, J 104 Interactions between Two Magnetic Dipoles: Orientation and Distance Dependence of the Bnergy of Magnetic Interactions 106 Summary: Structure and Energetics of Electeons, Vibrations, and Spins 108 References 108 “Transitions between States: Photophysical Processes 4109 ‘Transitions between States 109 A Stating Point for Modeling Transitions between States 111 ‘Classical Chemical Dynamics: Some Preliminary Comments 112 ‘Quantum Dynamics: Transitions between States 113, Perturbation Theory 113 “The Spirit of Selection Rules for Transition Probabilities 118) "Nucleae Vibrational Motion As a Trigger for Electronic Transition ‘Vibronie Coupling and Vibronic States: The Bffect of Nuclear Mi ‘on Electronic Bnergy and Electronic Steueture 119 “The Bifeet of Vibrations on Transitions betveen Electronic States: ‘The Franck-Condon Principle 122 A Classical and Semiclassical Harmonic Oscillator Model ofthe Franck-Condon Principle for Radiative Transitions (R + tv > "R and*R> Rly) 124 ‘A Quantum Mechanical Interpretation of the Franek-Condon Principle and Radiative Transitions 128 ‘The Franck-Condon Principle and Radiationless Transitions CR R+hea 130 Radiationless and Radiative Tr Different Multiplicity 134 ‘Spin Dynamics: Classical Precession ofthe Angular Momentam Vector 135 recession f a Quantum Mechanical Magnet in the Cones of Possible Orientations 139 Important Characteristics of Spin Precession 141 Some Quantitative Benchmark Retationships between the Strength of ‘Coupled Magnetic Field and Precessional Rates 142 ‘Transitions between Spin States: Magnetic Energies and Interactions 144 ‘The Role of Blectron Exchange (J) in Coupling Electron Spins 144 Couplings ofa Spin with a Magnetic Fick: Visualization of Spin ‘Transitions and Inersystem Crossing, 146 \ector Model for Transitions between Magnetic States 148 lions between Spin States of 321 3.22 323 3.24 325 3.25 327 44 4s 46 ar ax 49 410 aun 42 ana 44 4s 4.16 Contents Spin-Orbit Coupling: A Dominant Mechs Changes in Organic Molecules 149 ig of Two Spins with a Third Spin: T, > $ and T_—> $ ms 157 Coupling Involving Two Correlated Spins: Ty > $‘Transtions. 158 Inersystem Crossing in Diradicals, 1): Radical Pairs, KP), and Biradicals, (BR) 159 Spin-Onbit Coupling in (D): The Role of Relative Orbital {or Inducing Spin Oriontation 160) Intersystem Crossing in Flexible Bitadicals 164 What All Transitions between States Have in Common 166 References 167 188 ‘The Absorption and Emission of Light by Organic Molecules 169 ‘The Nature of Light: Series of Paradigm Shifts 169 tion and the “Ultraviolet Catastrophe" and of Light Energy: The Energy Quantum Is Planck's Quantizat Postulated 172 ‘The "Photoelectric Effect” and Einstein's Quantization of Light— ‘The Quantum of Light: Photons 173 IF Light Waves Have the Properties of Patcles, Do Particles Have the Properties of Waves? —de Broglie Integrates Matter and Light 176 Absorption and Emission Spectra of Organic Molecules: The Stato nergy Diagram as a Paradigm for Molecular Photophysics 178 ‘Some Examples of Experimental Absorption and Emission Spectra (of Organie Molecules: Benchmarks 178 The Nature of Light: From Particles to Waves to Wave Particles 181 A Pictorial Representation ofthe Absorption of Light “The Interaction of Electrons with the Flectic and Magnetic Forces of Light 182 ‘A Mechanistic View of the Interaction of Light with Molecules: ight asa Wave 184 ‘An Exemplar of the Interaction of Light with Mater: The Hydrogen ‘Atom * 185; [From the Classical Representation to a Quantum Mechanical Representation of Light Absorption by a Hydrogen Atom and a Hydrogen Molecule 188 Phoions as Massless Reagents 191 Relationship of Experimental Spectroscopic Quantities to Theoretical Quantities 194 The Oscillator Strength Concept 198Contents 417 4s 49 420 421 422 423 424 425 426 427 428 429 430 431 432 433 434 435 436 431 438 439 440 4a 442 “The Relaonshipbotwcen he Clesical Concept of OsiltorStength andthe Quin Mechanical Transition Dipole Moment 196 Examplesof he Relationships of, A2, 2, < WLP >, and 197 xpesimenta Tess of the Quantitative Theory Relating Enssion and Absomtion oSpectoscopi Qsanites 700 “The Shapes of Absorption and Emission Specta 201 “The Fanek-Condon Principle and Absorption Spectra of Orgone Molecules 203 “The aanck- Condon Principle and Emission Specie 208 “The Etec of Oia Configuration Mixing and Molpliciy con Radiative Teansiions 210 Experimental Bxemplars of the Absorption and Emission of Light by Organic Molecules 214 Absorption, Emission, and Excitation Spectra 215 Order of Magnitude Estimates of Radiative Transition Parameters 218 (Quantum Yields for Emission ((R-> RI) 223 Experimental Examples of Fluorescence Quanturn Yields 230 Determination of "State Energies” Es and Ey from Emission Spectra 234 ‘Spin-Orbit Coupling and Spin Forbidden Radiative Transitions 235 Radiative Transitions Involving a Change in Multiplicity: Sp-<> Tins) and So + (0°) Transitions as Exemplars 237 Experimental Exemplars of Spin-Forbidden Raclative Transitions: Sy T, Absorption and T,-> Sj Phosphorescence 240 Quantum Yields of Phosphoresvence, &p: The Ty —> Sp + hy Process 243 Phosphorescence in Fluid Solution at Room Temperature 244 Absorplion Spectra of Blectronically Excited States 243 Radiative Transitions Involving Two Molecules: Absorption Complexes and Exciplexes 247 Examples of Ground-State Charge-Transfer Absorption Complexes 248 Excimers and Exciplexes 249 [Exemplars of Excimers: Pyrene and Aromatic Compounds 253 Exciplexes and Exciplex Emission 256 ‘Twisted Intramoleet Emission from “Upper Excited Singlets snd Triples: The Azulene ‘Anomaly 260 References 262 ne ‘Charge-Transfer States 257 5 Sa 52 33 34 35 36 37 58 59 5.10 sar 53 5.4 sls 56 3.7 5.18 59) 5.20 521 5.22 523 528 525 Contents Photoplysical Radiationless Transitions 265 Photophysical Radiationless Transitions As a Form of Blectronic Relaxation 265 Radiationless Electronic Transitions asthe Motion ofa Representative Point on Electronic Energy Surfaces 265 Wave Mechanical Interpretation of Radiationless Transitions between States 270 Radiationless Transitions and the Breakdown of the Rom Oppenheimer Approximation 275 An Essential Difference between Strongly Avoiding and Matching. Surfacos 275 Conical Interséctions Near Zero-Order Surface Crossings 275 Formulation of « Parameterized Model of Radiationless Transitions 276 Visualization of Radiationless Tea Motion; Vibronic Mixing 277 Intersystem Crossing: Visualization of Radiationless Te Promoted by Spin-Orbit Coupling 281 Selection Rules for Intersystom Crossing in Molecules 282 ‘The Relationship of Rates and Efficiencies of Ratiationless| ‘Transitions to Molecular Suucture: Suetching and Twisting as ‘Mechanisms for Inducing Electronic Radiationlese Transitions 287 ‘The “Loose Bolt” and “Free-Rotor” Effects: Promoter and Acceptor Vibrations 288 Radiationless ‘Transitions between Large Energies 291 ‘actors That Influence the Rate of Vibrational Relaxation 295 ‘The Evaluation of Rate Constants for Radiationless Processes from, Quantitative Emission Parameters 295 Examples of the Fstimation of Rates of Photophysical Processes from Spectroscopic Emission Data 298 Internal Conversion (S, > Sy, $;> Spy Te +71) 300 ‘The Relationship of Internal Conversion to the Excited-State Structure of *R 301 ions Promoted by Vibrational fatching” Surfaces Separated by ‘The Energy Gap Law for Internal Conversion (S,-> $3) 303 ‘The Deuterium Isotope Test for Internal Conversion 304 Examples of Unusually Slow S, ~> 8, Internal Conversion 305 Intersystem Crossing from $,> Ty 306 The Relationship Between $; -> T, Intersystem Crossing to Molecular Steucture 307 “Temperature Dependence of $, + T, Intersystem Crossing 308. Ingersystem Crossing (P > $,) 309Contents 5.26 ‘The Relationship between T, ~ Sp Intersystem Crossing and Molecular Structure 309, 5.27 The Bnexgy Gap Law for'T, > Sp Intersystem Crossing: Devterium Isotope Effects on Interstate Crossings 310 5.28 Perturbation of Spin-Forbidden Radiationless Transitions 311 5.29 Internal Perturbation of Intersystem Crossing by the Heavy-Arom Effect 312 5.30. Extemal Perturbation of Intersystem Crossing 313, 5.31. ‘The Relationship between Photophysical Radiationless Transitions ‘and Photochemical Processes 314 References 315 \PTER6 A Theory of Molocular Organic Photochomistry 319 6.1 Introduction o a Theory of Organic Photoreactions 319 62 Potential Energy Curves and Surfaces 322 63 Movement of a Classical Representative Point on a Surface 323, 6A ‘The Influence of Collisions and Vibrations on the Motion of the Representative Point on an Energy Surface 325 6.5. Radiationless Transitions on PE Surfaces: Surface Maxima, Surface Minima, and Funnels on the Way from "R toP 325 66 A Global Paraligm for Organic Photochemical Reactions 326 67 Toward a General Theory of Organic Photochemical Reactions Based ‘on Potential Energy Surfaces 328 68 Determining Plausible Molecular Structures a Pathways of Photechemical Reactions 330 69 Tho Fundamental Surface Topologies for “Funnels” from Excited faces to Ground State Surfaces: Spectroscopic Minima, Extended face Touchings, Surface Matchings, Surface Crossings, and Surface Avoidings 330 6.10. From 2D PE Curves to 3D PE Surfaces: The “Jump” from Two Dimensions t0 Three Dimensions. 333, 6.11 ‘The Nature of Funnels Comtesponding to Surface Avoidings ‘and Surface Touchings Involved in Primary Photochemical Processes 334 6.12. “The Noncrossing Rule” and Its Violations: Conical Intersections and ‘Theie Visualization 335, 6.13, Some Important and Unique Properties of Conical Intersections 337 6.14 Diradicaloid Structures and Diradicaloid Geometries 341 615. Diradicaloid Structures Produced from Sieetching a Bonds and ‘Twisting x Bonds 344 Plausible Reaction 6.16 617 618. 619 620 626, 627 628 629 630 631 632 633 634 635 6.36 Contents ai An Exemplar for Ditadicaloid Geometties Produced by ¢-Bond ‘Sueching and Bond Breaking: Stretching ofthe © Bond of the Hydrogen Molecule 344 ‘An Exemplar for Diradicaloid Geometries Produced by 1-Bond ‘Twisting and Breaking: Twisting of the x Bond of Ethylene 348 Frontier Orbital Interactions As a Guide tothe Lowest-Energy Pathways and Energy Barriers on Energy Surfaces 351 “The Principle of Maximum Positive Orbital Overlap for Frontier Orbitals 353 Stabilization by Orbital Imeractions: Selection Rules Based on Maximum Positive Overlap and Minimum Energy Gap. 353 ‘Commonly Encountered Orbital Interactions in Organic Photoreactions 354 Selection of Reaction Coordinates from Orbital Interactions for "Ror R-> FP Reactions: Exemplars of Concerted Photochemical Reactions and Photochemical Reactions That Involve Diradicaloid Intermediates 357 Electoonie Orbital and State Correlation Diagrams 357 ‘An Exempla for Photochemical Concerted Petieyclic Reactions: “The Electrocyclic Ring Opening of Cyelobutene and Ring Closure of 1,3-Butadiene 358 Frontier Orbital Interactions Involving Radicals as Models for HalFFiled Molecular Orbitals 359 Orbital and State Corretation Diagrams 362 ‘The Construction of Electron Orbital an State Correlation fora Selected Reaction Coordinate 361 igrams for Concerted Photochemical wgrams ‘Typical State Correlation Pericyclic Reactions 364 Classification of Orbitals and States for the Bletrocyclic Reactions (of Cyclobutene and 1,3-Butadiene= An Exemplar Concerted Reaction 364 Concerted Photochemical Pericyclic Reactions and Conical sections 368 ‘Typical State Correlation Diagrams for Nonconcerted Photoreactions: Reactions Involving Intermediates (Diradicals and Zwitterions) 368 Natucal Orbital Corelation Diagrams 368 ‘The Role of Small Barriers in Determining the Efficiencies of Photochemical Processes 369) ‘An Exemplar for the Photochemical Reactions of n.x* States 370 ‘The Symmetry Plane Assumption: Salem Diagrams 372 ‘Au Exemplar State Conrelation Diagram for n-Orbital Initiated Reaction of n,7r° States: Hydrogen Abstevetion via a Coplanar Reaction Coordinate 372Contes ar 6.38 639 640 6a a2 chapren7 a 12 13 4 75 16 1 78 79 7.10 mm mm 713 14 a5 116 17 7.18 m9 Extension of an Exemplar State Coreation Diagram to New Situations 375 State Correlation Diagrams for «-Cleavage of Ketones 375, ‘A Standard Set of Plausible Primary Photoreactions for 17° and rng States 378 ‘The Characteristic Plusible Primary Photochemistry Processes of wx* Slates 318 ‘The Characteristic Plausible Primary Photochemical Processes of ve States 380 ‘Summary: Energy Surfaces as Reaction Graphs or Maps 381 References 382 Energy Transfer and Electron Transfor 383 Introduction to Energy and Electron Transfer 383 ‘The Flectron Exchange Interaction for Energy and Elect ‘Transfer 387 “Trivial” Mechanisms for Energy and Electron Transfer 391 Energy Transfer Mechanisms 396, Visualization of Energy Transfer by Dipole-Dipole Interactions: ‘A Transmiter-Antenna Receiver-Antenna Mechanism 399 Quantitative Aspects of the Frster Theory of Dipole-Dipole Energy ‘Transfer 400 ‘The Relationship off to Energy Transfer Eficieney and Separation of Donorand Acceptor Ry, 404 ‘Experimental Tests for Dipole-Dipole Bnergy Transfer 406 [Hleetron Exchange Processes: Energy Transfer Resulting from Collisions and Overlap of Blectron Clouds. 411 [lectron Exchange: An Orbital Overlap or Collision Mecha nergy Transfer 411 Flectron-Transfer Processes Leating to Excited States 413 ‘Tiplet-Triplet Annihilation (TTA): A Special Case of Energy ‘Transfer via Blecton Exchange lteractions 414 lectron Transfer: Mechanisms and Energetics 416 Mateus Theory of Electron Transfer 424 A Closet Look at the Reaction Coordinate for Electron Transfer 436 [Experimental Verifcation of the Marcus Inverted Region for Photoinduced Blecton Transfor 438 Examples of Photoinduced Electron Transfer That Demonstrate the Marcus Theory lt Long-Distance Blecton Transfer 441 ‘Mechanisms of Long-Distance Electron Tra ‘nd Phrough-Bond Interactions 442 of er: Through-Space 7120 721 722 123 104 125 726 121 128 129 730 Tal 132 Contents A Quantitative Comparison of’ Transfer 445 A Connection between I Transfer 446 Photoinduced Blectron ‘Transfer between Donor and Acceptor ‘Moieties Connected by a Flexible Spacer 447 ‘Experimental Observation of the Marcus Inversion Region for Freely Diffusing Species in Solution 448 Control of the Rate and Efficiency of Blectron-Transfer Separation by Contvolling Changes inthe Driving Force for Eletron Transfer 449 Application of Marcus Theory to the Control of Product Distebutions 451 ‘The Continuum of Structures from Charge Transfer to Free Fons: Exciplexes, Contact fon Pats, Solvent Separated Rascal Ton Pais, and Free lon Pairs 454 ‘Comparison between Exciplexes and Contact Radical lon Pairs 458 Energy and Electron-Transfer Equilibria 461 Energy-Transfer Equilibria 461 lectron-Transfer Equilibria inthe Ground State 463 Excited-State Blecuon-Teansfer Equilibria 463 -Excited-State Formation Resulting from Electcon-Tansfer Reactions: ‘Chemiluminescent Reactions 464 Role of Molecular Diffusion in Energy and Blectron-Transfor Processes in Solution 466 ‘An Bxemplar Involving Energy Transfer Controlled by Diftusion 467 Esimationof Rate Constants for Diffusion Contolled Processes 469 Examples of Neat-Diffusion-Controlled Reactions: Reversible Formation of Collision Complexes 472 iplet-Triplet Energy and Electton molecular Electron, Hole, and Triplet ‘The Cage Effect 474 Distance-Time Relationships for Diffusion 476 Diftusion Control in Systems fnvolving Charged Species 478 Summary 479 References 479 Y Photochemical Reaction Mechanisms 483 ‘Some Philosophical Comments Concerning the Fundamental Nature fof Reaction Mechanisms. 488 Creation ofa Standart Mechanistic Set 489 Use of Kinetic Plausbility in Quantitative Mechanistic Analyses 493Contents 85 86 a7 a8 89 810 aul 812 83) ad as) 816 alr 88) 819 820 sai 822 8.23, 824 825 826 827 828 Ievvocuction to the Reactions of Free Raclcals and Biradieals $01 ‘The Use of Structural Criteria for Mechanistic Analysis: ‘The Role of Reaction Intermediates (*R, 1) in Strctuce-Reaetivty Conelations 513 ‘The Use of Reaction Types and Structural Relationships in Mechanistic Analyses 514 ‘An Exemplac of the Use of Structural Relationships in Mechanistic Analysis 516 Rules for Proceeding from Rate Laws to Photochemical Reaction Mechanisms 518 Roles for Proceeding from Quantum Yields and Efficiency Lavrs to Kinetic Information on Photochemical Reaction Mechanisms 324 Experimental Methods for Determining Rate Constants of Photoreactions 527 Pulsed Excitation of R to Produce *R 528 “Techniques for Monitoring Upper Electronic States, "R529 Low-Temperature Matrix Isolation Techniques 530 ‘Two-Laser (Two-Color) Flash Photolysis. 531 ‘The LaserJet Technique 534 Stem-Volmer Analysis of Photochemical Kineties: Competition between Unimolecular and Bimolecular Deactivation of "R535 ‘Sterm-Volmer Quenching: Rate Constants from Bificiency versus Concenteation Measurements 537 ‘Stemn-Volmer Analysis Based on Data from Time-Resolved Measurements Using Gated Detection 539 Experimental Exemplars ofthe Measurements of Photochemical Rate Constants 540 ‘Measurement of Absolute Efficiencies in Determining Kinetic Parameters 547 Kinetics of Reactions Involving More Than One Exeited Stato $49 ‘The Peabo Method for Detecting Spectroscopically “Invisible” ‘Transients 552 [Experimental Measurement of the Efficiency of Radiationless Processes: The Photoacoustic Method 533 Reactive Intermediates: Experimental Detection and Characterization of Rand! 557 Applications of Time-Resolved Infrared and Magnetic Resonance Spectroscopic Methods forthe Characterization ofthe Staucture and Dynamics of *R and I: The a-Cleavage Reaction of Ketones as an Exemplar 560 Investigation ofthe Structure of *R by Time-Resolved Infrared Spectroscopy (TRIR) 562 Investigation of the e-Cleavage *R > T(RP) Process by TR IR 564 829 830 831 332 833 834 835 836 837 838 839 840 Bal 8a 843 844 845 8.46 847 848 849 830 851 332 833 854 Contents xs Time-esolved Eecton Paramagnetic Resonance and CIDEP 64 ection Spin Polarization: Deviation fom the Boltzmann Distribation of Spin and ts Eet on the Inensies of Magnetic Resonance Signals 565 Investigation of the Structure of “R(T, and the Mechanism af he Si> R(T) ISC by TREPR 567 Investigation ofthe Photochemical Primary Process *R-> I Pacess by TREPR 570 The Direct Observation of KRP)jeq and BR) by TREPR 572 Experimental Test forthe Involvement of Electronically Excited States “R: Qualitative Aspects. Decicing betveen "R(S) and *Rr) 972 -Bxperimental Tet for the Tovolvment of Eletronically Excited States (RY: Quantitative Aspects 375 ‘The Use of Kinetic Methods to Detect aud to Hetty Reason Intermediates, *R and 1379 Reactions Involving BiadicalIntemecintes 585 Spin Chemise Spin Selection Rees for Chemical Reactions 593 Magnetic fects on Reactions of 1(RP) and (BR) 585 Kinetic Basis for Magnetic Feld Etec (MIFE, Magnetic Isotope Effcets (MIE) and Chomicll Indaced Dynamic Nucor Plaiaton (CIDNP) 396 ‘Magnetic Field Bffects on the Reactivity ane Products of (RP) and SBR) 597 Magnetic Isotope Bets onthe Reactivity and Products of (RP) and *{(BR) 602 Chemically Induced Dynamic Nuclear Polarization of Racal Pas: ‘The Nuclear Spin Oriematan Dependence of Chemical Rest of HRPjag 606 CIDNP of Conformational Feb Bratcals 612 Cerca Spectroscopy: The Use of Photochemical Resins to Measure Excited-Sat Energetics and Dynamics Advances in Modem Mechanistic Organic Photochemistry Uttatest Reactions snd Laser Coherent Photochemistry 617 Femiosecond Photochemisiy 618 Singl- Molecule Spectroscopy 618 Coherent Laser Photochemistry 619 Muliphoton Microscopy 619 Some Fxemplar Sst Energy Paramctrs 620 Ketones 620 Alkenes ad Polyenes 621 Conjugated Foones and Dienones 622Contenis 8.55 Aromatic Hydrocarbons 622 856 Summay 623 References 624 cnaprer 9 \lochemistry of Carbonyl Compounds 629 9.1 Introduction tothe Photochemistry of Carbonyl Compounds 629 9.2 Molecular Orbital description of the "R(a,r*): Primary Processes of Carbonyl Compounds 630 93 The *R(n,z*) > I Primary Photoche Frontier Orbital Interactions 632 94 ‘The L-> P Secondary Thermal Processes Based on Radical Pair, Free Radical, and Biradical Resctions 634 9.5 The Alkoxy Radical: A Close Analogue of the Reactive n,x* Carbonyl Chromophore 636 9.6 State Energy Diagrams for Ketones 637 9.7 The *Rinyn*) ~» P Processes of Ketones and Aldehydes 639 98 An Exemplar of an n < HO Initiated *R¢a,zr*) + 1 Process: ‘The Primary Process of Intermolecular Hydrogen Absteection 640 99 “Invisible Transients" in Radical-Radical Combination Reactions: ‘Teansionts Formation by Radical-Radical Combination that Revert Back o Stating Materials. Gat 9.10 “The Primary Process of Intermolecular Electron Transfer: Reaction of m,x"* States With Amines 613 9.11 Steuctuce-Reactivity Relationships in Intermolecular Hydrogen Absteaction 646 9.12 ‘The Primary Process of Electron Abstraction: Reactive T(x, State 650 9.13. Competition between Hydrogen and Electron Abstraction: Effect ‘of Variation for Orbital Stuctare and Hydrogen (Flectron) Donor Structure 650 9.14 The Primary Photochemical Process of Intramolecular Hydrogen ‘Absteaction: Norrish Type II Reactions 652 9.15. Reactivity and Bficiency Relationships in Type I Reactions 653 9.16 The Product Forming [(BR) -> P Step in Type II Reactions: A Paradigan forthe Behavior ofa 1-Biradieal 655 9.17 Geometry of y-Hydrogen Abstraction and ts Consequence on Competing Primary Photochemical Processes 657 9118 ‘The role of Intersystem Crossing in Deter Diradicals Produced by y-Hyelogen Abs 9.19 Beyond y-Hydrogen Abstraction: inramolecalar La-Hlydogen Absieiction 664 I Processes Based on 9.20 921 922 9.23 924 925 9.26 927 928 9.29 930 vai 9.32, 933 934 9.35 936 937 938 charren to 10.1 10.2 103 104 105 Contents ‘The Primary Process of «-Cleavage of nar* States: Aeyelic Ketones 665 ‘The Primary Process of e-Cleavage from nsr* States: Cyclic Ketones 668 Reactions of Primary Radical Pair Produced from a-Cleavage 669 Photochemistry of Cyclobutanones: A Special Case of arCleavage 672 ‘The Primary Process of «-Cleavage of ne* states, Structure Reactivity Relationships 673 An Orbital Model fora-Cleavage 677 ‘The Primary Process for Addition of n.* States to Blecron-Rich C=C Bonds 678 ‘The Primary Process of Addition ofn.x* States to Electron-Rich (C=C: Reaction Intermediates 680 Evidence fora Biradical Intermediate 682 Pdo-Fxo Selectivity Daring Photoaddition of Excited Casbonyls to Olefins 683 Examples of (2 +2] Cyeloadditon for nzx* States to Electron-Poor Etlytenes: An Example of axr*—> a Interaction 684 Stereoselectivity of the [2 +2] Cyclosddition of nva* States to Emylenes 688 Intramolecular (2 +2} Photocyctosddition 690 Examples of Photorearrangemients Initiated by f-Cleavage Followed by Combination and Disproportionation 691 Photochemical Fragmentations Initiated by Cleavage 694 ‘Synthetic Applications of the Photoreaetions of Carbonyl Compounds 696 Applications of the Photochemistry of Carbonyl Compounds in Photoimaging 698 Applications ofthe Photochemistry of Carbony! Compounds in Designing "Phototiggers” and “Photoprotecting Groups” 700 ‘Summary: The Photochemistry of Carbonyl Compounds 701 References 702 Photochemisty of Olefins 705 Introduction to the Photochemistry of Olefins 705 Molecular Orbital Description ofthe *R(ir,r*) Primary Processes of Olefins 706) ‘The 1+ P Secondary Processes of Alkenes 709 Exemplar State Energy Diagrams for Alkenes 710 ‘The cis-trans Isomerization: & General Process for Both $,(x,*) nd Ty(rat*) of Alkenes 714Contents tos lo7 tos. 109 10.10 lo. 10.12 103 10.4 10.15 1016 10.17 10.18 10.19 10.20 10.21 1022 1023 1024 1025 1026 1027 1028 1029 1030 ost 1032 10.33 ‘The cis-tras Isomerization of Acyclic and Cyclic Alkenes 715, ‘The cis-trans Isomerization of Conjugated Polyenes: The Nonequilibrating Excited Rotomers Principle “716 “The cis-trans Isomerization of Aryl-Substituted Alkenes 721 A Case Study of eis-trans Isomerization of Stilbene 722 Adiabatic eis-trans Isomerization in Sa 2"): Examples of *R > *P Processes 724 ‘Trapping of Strained crans-Cycloalkenes from cis Cyeloalkenes 726 ‘The cis-trans Isomerization through Conical Intersections 729) Intramolecular Pericyelic Resotions of the $\(,7°) States of| ‘Alkenes: Examples ofthe S(r,x") -> F—> P Provesses 730 Blectrocyelic Ring Openings and Ring Closures Involving I3-dienes 731 Blectroyelic Ring Openings of 1,3-Cyelohexs Closures of 1,3,5-Hexatrienes 736 Other Elecrocyelic Reactions of Tienes 739 lectrocyeli Ring Closures of Stilbenes and Related Systems 740 ‘Sigmatropie Rearrangements of the $7) States oF Alkenes 743 ‘The Di-z-methane (Zimmerman) Reactions: A Sigmatiopic Reaction ‘of Wide Scope 745 Di Di-remethane Reactions: Rigid Cyclic 14-Dienes and Related Compounds 748 ‘The [n +m] Photocyclonddition Reactions 751 ‘The [2 4-2} Photocycloaddition Resctions: Alkenes 752 ‘The [2 +2] and [4 +2] Photocycloaddition Reactions of 1.3-Dienes 754 Intramolecular Photocycloadditions of Alkenes and Polyenes 757 ‘The (2 + 2}Photocycloadiiion Resctions: Aryl Alkenes 760 Poton-Transfer Reactions from S(7,"):Zwitterionic Photoaddition Reactions 763 ‘A Comparison of then,” State Reactions of Carbonyls and Ty(rre*) States of Alkenes: Hydrogen Abstraction Reactions of Ty(r,2") States of Alkenes 764 £B-Cleavage Reactions 767 Cleavage Reactions 767 Photoinduced Electron-Transfer Reactions Involving Alkenes: Examples of "R-> ID", A**) Processes 768. Structure and Reactivity of Radical Cations and Anions 769 Pathways to Radical Cations and Anions of Alkenes 770 snes and the Ring methane Reactions: Acyclic L/-dienes 746 1034 1035 1036 10.37 10.38 1039 1040 loa 1042, 1043 104s 1045 10.46 10.47 10.48 ‘onapren 11 Pho ma na 13 14 us us ug ns ng H10 Contents Reactions of Alkene Radical Ion Paits: Addition of Amines 770 Generation of Alkene Radical Cations 772 Choice of Electron-Transfer Sensitizers 773 Gonetation of Alkene Cation Radicals: Maximizing the Yield of Radical lon Pai Formation 777 Reactions of Atkene Cation Radicals: Geometric omerization 778 Reactions of Atkene Cation Radicals: Addition to Nucleophiles 780 Reactions of Alkene Cation Radicals: Dimerization 781 Reactions of Allene Cation Radicals: Intramolecular Cyclization 783 Applications of Photoinduced ci. ‘Systems 784 “The cis-trans Isomerization a a Photoswiteh 787 “The cis-trans Isomerization as a Photoregulator of Phase Transitions fan Isomerization in Biological Jon Transport through Membranes through cis omerization 791 Application of cis-trans Isomerization in Laboratory and Industral Symheses 792 Application of Photoinduced Pericyctic Rea Summary 796 References 797 us 794 Photochemistry of Enones and Dienonos: 801 Introduction to the Photochemistry of Enones and Dienones 801 Molecular Orbital Description ofthe *R(n«*) and *R(r7*) States ‘of Enones: Primary Processes of Enoaes and Dienones. 801 ‘The I> P Secondary Processes of Enones and Dienones 803 ‘Exemplar State Energy Diagrams for Enones and Related Structures. 803 ‘The Photochemistry of 8,y-Enones: Exemplas of the Photochemistry ‘of Enones With Isolated But Proximate C=O and C=C Bonds 805 Photochemistry of then,7* States of f.y-Enones 806 Comipetition between the Reactions of nyt" and 7° States of Enones 808 Competitive Reactions from the Ty(r,*) States of f.y-Enones: Oxe-dis-anetane Rearrangement and cis-teans Isomerization $LO Introduction tothe Photochemistry of ,f-nones 814 Photochemistry of «,A-Enones Originating inthe Ty(a,7") State Analogies with the Primary Processes ofthe n,x* States of Carbonyls 815,Contents nua nae 1143 a 1s 11.16 nay 118 mus 1120 nat n22 chapren 12 a 2 123 124 1s D6 aa bs 29 12.10 a Photochemisiry of yB-Enones Originating in the Ty(0") State: Analogies to the Primary Processes of the x2" States of Alkenes B18 ‘The Sigmatropic Rearrangement of Cyclohexenones: Type A and B Rearrangements $20, Role of Geometric Isomerization in the Type A Reaction of 2-Cycloherenones 821 ‘Type B Rearrangement of 2-Cyctohexenones: The [1,2] Aryl and [1.2] Vinyl Migeations Stating from a T\(n,x") State $23 ‘The [2 42} yclonddtion Reactions of Cyelic f-Enones $24 ‘Sigmatropic Rearrangements of Cross-Conjugated Dienones 827, Photochemistry of Linear Conjugated Cyclohexadienones the [Ge] Electrocyctic Ring Opening and [1,2] Sigmatropic Rearrangement 832 ‘Syntictic Applications of Fuone and Dienone Photochemistry 833 Developing Useful Synthetic Methodologies for Construction of Diastereoseletive and Enantioselective Cyclobutane Rings 838 Photocycloaddition Resctions of Coumarin and Psorelen, Psoralen Uluaviolet A Treatment 840 Photocycloaddltion Reactions of Nucleic Acid-Base Cancer 842 Summary 843 References 844 and Skin Photochemistry of Aromatic Molecules ear Introduction to the Photochemisty of Aromatic Molecules 847 ‘Molecular Orbital Description of the *R(r,*) Primary Photochemical Processes of Aromatic Molecules 848 ‘Tho Primary Photochemical Processes of Aromatic Molecules 850 Exemplar State Energy Diagrams of Aromatic Molecules. 851 Pericyclic Photochemical Reactions: Blectrocyetic and Related Reactions of Aromatic Nuclei 853 Pericyelic Photochemical Reactions: [6c] Klectrocyclization 856 Aryl-Vinyl Di-s-methane Rearrangement 858 Photocycloaddition of Aromatic Molecules: Photocyclodimerization 860 Photocycloaddition Reactions of Benzene and is Derivatives 863 Photocycloadtion Reactions of Benzene and Is Derivatives: ortho or{2+2]Cyclolitions 864 Photocycloaddition Reactions of Benzene and Is Derivatives: meta or [2 4-3} Cyeloaddition $67 12.2 3 12.4 1245 12.16 12.17 12.18 ray 1220 1221 12.22 12.23 1208 12.25 1226 1227 12.28 12.29 120 pat 1232 1233 1234 1235. Contents Photocycloadition Reactions of Benzene andl Its Derivatives: Competition between [2-+ 2} and [2 +3} Photocycloadlition 870, Photocyeloaddtion of Polycononsed Aromatic Molecules: Addition oOlefins 872 Homalytic f-Cleavage of the C—O Bond of Aryl Esters and Related ‘Compounds: The Photo-Fries and Related Rearrangements 875 Homalytic f-Cleavage of the CC Bond of Small Rings 878 Heterolytic B-Cleavage: Photosolvolysis and Related Reactions 879 Excited-State Acidity and Basicity: Base-Assisted f-Cleavage (r-O-H) 883 Homolytica-Clcavage of Aryl Halides: Aryl-Aryl Coupling 886 ‘Hlecivon-Transfer Reactions: Addition to Amines 888 Aromatic Molecules as Electron Transfer Photosensitizers of Radical Cation Formation 850 Photochemical Electophilic Aromatic Substitmion: Proton-Transfer Reactions of Aromatic Molecules. 893 Photoinduced Nucleophilic Aromatic Substitution via a Photoinduced Blectron-Trausfer Process 894 Photoinduced Nucteophilic Arematic Substitution Involving Direct, ‘Attack of Nucleophile on *R: The SyAr* Mechanism (Substitution, Nucleophitic, Excited State) 896 Photoinduced Nucleophitic Aromatic Substitution Involving Blectron “Transfer from Nucleophile to °R: The Sy(et)Ae* Mechani (Substitution, Nucleophili, Plectcon Transfer, Excited State) 899 Nucleophilic Substitution via Syg-Ar* Mechanism (Substitution, Radical Anion, Nocleophilic, Excited State) 904 Photoinduced Nucleophilic Aromatic Substitution Triggered by Photoionization: The SyqsAr" Mechanism (Substitution, Nucteophitic, Radical Cation, Excited State) ‘Summary of Photoinduced Nucleophlie Subst Synthetic Applications ofthe Photochemistry of Aromatics 907 Potential Applications of the Luminescence Propesties of Aromatic Molecules: Molecular Luminescence Probes 911 Polarity Probes Based on the Ham Bffect 912 Polarity Probes Based on the Twisted Intramolecular Charge-Transfer Phenomenon 912 Viscosity Probes 915 Viscosity Probes Based on the TICT Phenomenon 915, Fluorescence Thermometers 916 ‘Fluorescence Thermometers Based on a Temperature-Dependent Radiationless Process 916scot Contents 1236 1237 1238 1239 1240 cHapren ta BI 182 133 BA Bs 136 Ba 18 9 13.10 1B 1312 Ba3 Fluorescence Thermometers Based on Excimer and Excited ‘Monomer Equilibrium 917 Fluorescence Thermometers Based on the TICT Phenomenon 917 Fluorescent Chemosensors 918 Fluorescent Chemosensors Based on Blectron Transfer Principles 919 Summary 920 References 921 ‘Supramolecular Organic Photochemistry: The Contral of Organic Photochemistry and Photophysics through Intermolecular Interactions 925 “The Curent and Emerging Paradigm of Supramolecular Orgone Chemisty 925 ‘Paradigm of Supramotesalar Organic Chemistry: guest @host Complexes 928 “Toward Paradigm for Supramolecular Organic Photochemistry 930 {An Enzyme as an Exemplar Supeamolectlar Host for gust@host Complexes, Contol of Activation Parameters and Competitive Reaction Rates through Supramoleculac Effects 933 Extending Some of the Key Structural and Dynamic Features of vest @ezyme Comples to Organic guest @hest Complexes. The Fost Renton Cavity Concept 938 Some Exemplar Organic Hess for Aqieons Solution Sprameteclar Photochemisy: Supercages, Cavan, and Capsules 981 Some Exemplar Host of Supramolecular Photochemistry in the Sold Stat: Ceystats and Porous Solids 948 “The Role of Tine Seale and Dynamics in Supramolecular Organic Photochemistry. The Transient and Persistent Spramolecslae Complex Concept. Hemicareplexes and Carceplexes 951 Supramolecular Control of Photochemical and Photophysical Processes: General Principles 954 Supramolecular Conta of Unimolecular Photophsical rocestes by Preorgaization of gust@host Complexes: Enhancement of Room ‘Temperature Phosphoresence 955 Supramolecular Col of Bimolceular Photophysical Processes by reorganization of guest@ost Complexes: Enhancement of Formtion of R959 Supeamoleula Cont of TipltTeiplet Energy Tiasfer through the Walls of «Carcerand Host 962 Supramolecular Coniol of Uniolecutar Photochenical Processs by Procgnization in gest @host Complexes: Supramolecular Seloatvty of he Reactive State 964 1B.4 13.45 13.16 13.17 1318 13.19 1320 1321 1322 1323 1324 chapren 14 Ma 2 M43 4a us 46 lag us Contents xsic ‘Supramolecular Contol of Unimolcculae Photochemical Processes by Preorganization of guest@host Complexes: Supramolecular Selectivity ofthe "R > I Processes 965 Supramolecular Chiral Effects on Two Competing Primary Processes (of 'R Involving Biradical Intermediates: Preorganization in _guest@host Assemblies 970 ‘Supramolecular Effects on Bimolecular Primary Processes reorganization through Orientational Effects in guesUeaguest@host Supramolecular Assemblies 972 ‘Supramolecular Effects on *R in the Solid State: Preorganization {hough Conformational and Orientational Control inthe Solid State 976 ‘Supramolecular ects on *R: Templated Photodimerization inthe Solid State 977 ‘Supramolecular Chiral Effects on *R in Concested Reactions and Reactions Involving Funnels: Preorganization in guest@host Assemblies 979, ‘Supramolecular Effects on Reaction Intermediates I: Mobility Control on I@host Assemblies 981 ‘Time-Dependent Supramolecular Effects on Reaction Intermediates © 987 ‘Supramolecular Effects on Products (P@carcerand)y: Stabilization of Reactive Product Molecules (P) 993 ‘Supramolecular Effects on Reactive Intermediates (1@carcerand): Making Transient Intermediates () Persistent though Incarceration 995, Summary 996 References 997 Molecular Oxygen and Organic Photochemistry 1001 ‘The Role of Molecular Oxygen in Organie Photochemistry 1001 ‘The Electronic Structure of the Oxygen Molecule: Ground and Excited States 1003 ‘Thermodynamic and Blecrochemical Properties of Oxygen and ‘Oxygen-Related Species 1008 Interaction of Oxygen with the Ground States of Organic Molecules 1012 Interaction of Ground-State Oxygen with Electronically Excited Singlet States, “R(S,), of Oxganie Molecules 1012 Quenching of Excited Triplet States (1) by Oxygen: Energy- Tranter Processes 1015 ‘Mechanism of Tilet Photesensiizaton of Singlet Oxygen Generation 1018 CCharge-Transfer Interactions in the Triplet Quenching Process 1020Contents 149° Efisieney of Singlet Oxygen, OA), Generation: Selecting « Good Singlet Oxygen Sensitzer 1022 14.10 Specuoscopy and Dynamics of Singlet Molecular Oxygen: Dynamics ‘of Radiative and Radiatontess Processes in Singlet Oxygen 1023 14.11 Physical and Chemical Quenching of Singlet Oxygen 1026 14.12 tmtermotecular Interactions Leading othe Radiationless Deactivation of Singlet Oxygen (Physical Quenching) 1026 14413 Intermolecular Interactions Leading to Chenncal Transformations (Chemical Quenching of'0,) 1027 IMM The Reversible (4+ 2} Cylon Reaction of 10,1 14-Dienes and Aromatic Systems 1029 145. Theene Reaction: An Important Tool in Organic Synthesis 1030, 14.16 Chemical Quenching of Excited Triplet States by Oxygen 103 14.17 Reaction of Oxygen with Reaction Intermediates, 1) +O: Mechanisms and Kinetics 1032 1418 Free Radical Savenginghy Oxygon:1(FR) +O,» Peroxides 1033 1419 Bitacical Scavenging by Oxygen: I(BR) +0,» Products 1034 1420. Reactions of Carbenes with Oxygen 1036 1421 Molecular Oxygen and Other Reaction Intermediates 1038 14.22. Motecular Oxygen in Biology 1038 1423_Is Evidence for Oxygen Quenching of Reaction Good Evidence for TipleInolvernent? 1039 1424 Summary 1040 References 1040 hapten 15. A Goneralzaton of the Photochemistry — orga ones, 15.1 Paradigm and Stratexy for Understanding the Photochemisty of Organic Functional Groups 1083 152 Some Examples ofthe Extension of the Paradigms of Scheme 15.1 to “Other *R" and “Other I" 1046 153 Photochemistry ofthe Nitro (R—-NO;) Functional Group 1017 1SA The Azo (-N=N—) Functional Group 1019 155. TheDiazo (RCN;) Chromophiore 1050 18.6 The Thioketone (R,C=S) Group 1051 15:7 Summary 1053 References 1053 Index 1055 Preface ‘Modern Molecular Photochemistry af Organic Molecules isa comprehensive, stan alone text that teaches students and researchers how to apply the paradigms of molec ular organic photochemistry to an understanding of the mechanistic and synthetic applications of organic photoreactions. After an intcoduetion to the fundamental prin ciples of the photophysics and photochemistry of organic molecules, the spectcoscopie techniques for determining organic photochemical mechanistus are deseribed in some detail with numerous exemplars. The role of spin chemistry in controling photo chemical pathways i also described in detail. The functional group or chromaphore approach is used to examine, classify, and understand the photochemical reactions of ccubonyls, olefins, enones, and aromatic compounels a terms ofthe paradigms in the {ntoduction ofthe book. For the first time, supramolecular organic photochemistry is described from fundamental principles of intermolecular interactions using a guest ‘noncovalently bonded to a host asa paradigm. The text concludes with a chapter on the role of singlet oxygen in organic photoreactions and a chapter on how toextend the paradigms described in the earlier chapter to achieve an understanding of essentially any organic functional group. Level and Approach ‘Thogoal ofthis textbook sto familiarize both students and sesearchers withthe critical ‘concepts an methodology involved in the investigation of organic photochemical reactions. A simple paradigm a the start of each chapter is elaborated with exemplars ‘that provide the student with an understanding through examples of the underlying. principles. The w bbe unierstood easily by students with the Fandamenta knowledge of college general chemistry, orgonic chomistey, and physi. Animportant feature of the book is avoidance of complex mathematics and the translation ofall concepts into familiar visuatized representations. These representations provi ‘complete and unified theoretical background for an understanding of light sbsorption and emission, or radiationless processes and photochemical reactions. For example,Preleco the eonceptofelecttonicenergy surfaces coupled with simple molecular orbital theory ie used to visualize the triggers of photochemical processes and the analogies that intellectually reduce the thousands of organic photochemical reaetions to a handful of fundamental primary photochemical reactions from electronically excited states. ‘This book will bof use to stadents interested ina qualitative, pictorial interpretation fof spectoscopic processes involving the absorption and emission of ight by organic otecules and the photochemical processes tha result from light absorption “Any new updates, supplements or erata pertaining o this book canbe found om ts bookpage at wwvwascibooks.com. History [As abit of history, it hos been over three decades since the publication of Moder Molecular Photochemistry (MMP). Ducing tis period, the concepts and paradigrs “Gccerbed in MMP have become part and parcel of modem synthetic and mechanistic photochemistry, and have been absorbed as routine intellects! tools ina wide range bf elds, including physical organic chemistry, chemical biotogy, polymer chemisty, snaterials science and nanoscience. Remarkably, nostof the basic paradigms of MMP remain the bedrock of eurrent mechanistic analyses, investigations, and application Of photochemical reactions. However, the elaboration of these paradigms by the effect of spin and electron transfer Was nat covered in MIM. It was decided that « textbook, which nehuded these factors ndintegrate them withthe general successful jedagogeal philosophy of MME, wou be of ws and interest to not only practicing Hhotocemists andthe students, but also to thse in a variety of other lds (6 biology scientists, polymer scientists, materials scientist, and isis) who integrate photochemistry and photophysics into their research and teaching. “A pier, Principles of Molecular Photochemistry: An Introduction, published in 2009 consisted of seven chapters that inttodueed photochemical and photophysical Concepts from a small se of principles that are Faniar and understood by stents Gf chemistry and ther sciences. An initial paradigm is introduced that relates the photon and a reactant molecular structre to photochemistry through the structure pr electronically excited states, reactive intermediates, and products. The same parse tiga is realy adapted toincorporate the photon anda reactant molecular structure ke ‘hotophysies. The ole of electronically excite states, and electonie-virational and eetronic-spin interactions are clearly described in pictorial terms that canbe readily “aerstood and applied to systems of interes. Fr the fist ime in any photochemical texts fundamental description of electronic spin and its impaet on photochemical and photophysical processes is described with an intuitive, pctv, and powerful vector vrodel, The mysterious processes of spin-orbit coupling, intersystem crossing, and tnagnetic effects on photochemical and photophysical processes arc realy handled Wh this model. Also, forthe irsttime inany photochemical text, the concepts of clec~ Tronic energy teansfer and electron transfer treated from a common foundation and fet of eonceps, The tremendous progress in theoretical and experimental aspects of ‘leetron transfer i covered in depth and will be of great assistance as an introduction Preface tlie toca spect mot sa poten. bok, Mader tec sur Poche of rg eens seen gs he pine From th pts ths carly chopte te fea er esr ed Soerin do mean ea yey atau ni Acknowledgments "sts a wh cons a Kes cn One owen. The 2 red tthe many stn re groups wh have ait in ie vee of ee ah hing a aig eons 25 sp nisin scr ui acon, Nee any colleagues who allowed cir “info be pike” a thereby en th hors opie tasaton af rus atten coneptins cneee cent pens ih tng tet Nowe tio een comm datetime once cok project hatte mic longer ne than we rah iglesia. Spec saat Sts or Un ae Siu Ose olor aston ng df tk Tn no aie llwt ens wore pied eal comes seston RSs PD Leni ann: ea A ee ih shad for eting vs on many execs publications and discussions. . Pee Geert ‘Theatr hve bon bested and esto and nppored oughou the dv of wi isc eons tn Creonnapemet ad pti of Be Ae isn oes of Ue Soe Ho Ty wi an) i ting of he comps manip, J. Cho, Web co ‘for the art production; and J. Snowden and P. Anagnostopoulos for tra - forming the manuscript into the final product, It was a woné i ; famine prod Is wont nt piu Ech ofthe ators thnk, profoundly, oo wires and anisole sadcancnpting oh sags esd big he eyo dees nw he pine and Nicholas J. Tureo V. Ramamurthy 4.€, SeaianoModern Molecular Photochemistry of Organic MoleculesCHAPTER Molecular Photochemistry of Organic Compounds: An Overview 1.1__What Is Molecular Organic Photochemistry? Molecular organic photochemistry is @ science concemed with the structures and dynamic processes that result from the interaction of light with organic molecules. ‘The fleld of molecular exganic photochemistry can be conveniently classified in {erms of the photophysies of organic compounds (ihe interactions of light and oF ganic molecules resulting in net physical changes) andthe photochemistry of organic ‘compounds (he interactions of light and organi molecules resulting in net chemi cal changes), The molecular photochemistry of organic molecules is a rather broad. and interdisciplinary topic embracing the fields of chemical physies, molecular spec: {woscopy, physical organic chemistry, synthetic organic chemistry, computational or ‘ganic chemistry, and supramolecular organic chemistry. ‘In simplest terms (Scheme 1.1), molecular organie photochemistry involves the overall process R + liv > *R P, where R is an organic molecule that absorbs 1 photon (hu), whose frequeney (v) is correct for light absorption by Rj *R is an clecteonically excited molecule; and P is an isolated product (or products). Organic photophysies, on the other hand, involves the overall process Rt fy > *R > R, ‘where K absorbs a photon, but does not undergo any net chemical change. In general, R will stand not only forthe eactant molecule (R) that absorbs the photon, but also ‘any other molecules (M) that are required for production ofthe product (P). If not sited explicily, it should be assumed thatthe reactions described in this text are ‘conducted in a Solution of an inert solvent at or near room temperature (~ 25 °C) ‘The electronically excited molecule ("R) is the essential species that is universal all photochemical and photophysical processes. "The text describes how the overall photochemical process R-4-hv > P and the ‘overall photophysical process I+ hv > R can be visualized in structural, mech ‘anistc, theoretical, and experimental terms. For example, Scheme 1.1 describes a ‘lobal paradigm for understanding the possible paths forthe photochemical provess 'CChepter 1 Molecular Photochemisty of Oigante Compauinds: An Overvows Rtpy ——> ‘a——» fF ——+ p i+ ["1or*P} jue Scheme 1.1 A global paradisin for onganic photochemical reactions. Photophysical processes that retuny "R to Rare not Incuded at this pint, for simplicity. The *R > R plotphysical processes ace shstn in Scere 21 R-+ fv P. The holy geil of molecular organie photochemistry uses Scheme 1.1 and its plausible elaborations for she achievement of a complete structural and dy- naniic mechanistic description ofall ofthe physical and chemical steps hat occur as ‘the result ofthe absonption ofa photon by an organic molecule (R) and eventuate in ‘the formation of an isolated product (P) or the regeneration ofthe starting material (2). The nature ofthe species [and F will be discussed in Seetions 1.9 and 1.10. Scheme L1 and itselaboration for photophysieal processes (R + hv > R) provide a paradigo of remarkable versatility and scope that serves as a basis for analyzing all ‘organic phorachemical reactions and all photophysical processes. We shall employ the term “molecular photochemistry” to include both the photophysies of °R and the photochemistry of *, since the concepts and laws of photophysies and phatochem- istry ac intimately inerwoven. Indeed, we shall see that it i impossible to have a ‘roper understanding of the photochemical processes of "R without a corresponding, ‘understanding of the photophysical processes of *R Scheme I.1 shows that there are dee Fundamentally di primary photochemical processes, inct pathways, termed °R may follow on the way (oP: 1 A pathway, “R-> I» P, that leads to the formation of a discrete reactive intermediate () that can typically be descsibed as having the charscteristies of radical pair (RP), a biraical (BR), ora zwitterion (2), 2. A pathway, “R > F— P, that doesnot involve a disereterenctive intermediate (), but instead proceeds through a “Funnel” (F). This pathway takes R to P andl can be described in the language of energy surfaces asa “conical sueface intersection” or asa minimum produced by surface-avoided intersections, 3. A patwvay, °R->*1-> Por*R->*P -> P, that involves the formation of an ly excited dutermediate (1) or an electeonicaly excited product Of these three possibilities, *R -> I (RP, BR, or 2) isthe most commonly observed pathyray for oganie photochemical reactions. ‘The “molecular” part of molecular phovochesnstry emphasizes the use of molec- ‘lar structure and its implied dynamics (tansitions between states) andl molecular substiucture (electron configuration, nuclear configuration, and spin configuration) ular Organic Pholochomisty? Section 1.8 Why Study Mal ‘the crucial and unifying intellectual units for onganizing and describing the poss- bie, plausible, and probable pathways of photochemical reactions from “cradle” (he absorption ofa photon by a reactant, R, to form *R) to “grave” (the isolation of a product, P, produced by one of the three pathways from *R shown in Scheme 1.1, 1.2. Learning Molecular Organic Photochemistry through the Visualization of Molecular Structures and the Dynamics of Their Transformations “This text attempts to teach effective cognitive and contextual strategies for learning ‘molecular organic photochemistry. Physical organic chemistry has thrived and pro- _gressed rapidly because ofa tradition of correlating molecular structures with reaction ‘mechanisms and with chemical reactivity. Molecular structure provides a powesful andefective visual means of coupling molecular dynamics tothe change of molecular structure, We strive to provide an understanding of photochemical reactions through the visualization of molecular structure and the molecalar dynamics ofthe processes described in Scheme 1.1 1.3 Why Study Molecular Organic Photochemistry? ‘Scheme 1.1 displays schematically, at an elementary eve, the structural and dynamic: ‘content that is important for the study and understanding of modem molecular or- ‘ganic photochemistry. Every organie photochemical reaetion can be understood and ‘described in terms of the paradigm of Scheme 1.1 or some plausible and straight- forwacd modification or elaboration of Scheme 1.1. The motivation for studying the ‘molecular photochemistry of organic compounds depends on the context in which the student views the content of the field, and many different motivations ean provide such a context For example, there is the pure intellectual satisfaction of understanding how to visualize the ways in which two ofthe most fundamental components ofthe universe, photons (hv) and molecules (R), interact with one another to produce anelectronically excited molecule (°R), which eventually is transformed to an isolated product (P). particulag, there can be a special intellectual delight in earning how to integrate dfer- entfields, such as spectroscopy, quantum mechanics, reaction mechanisms, molecular structure, magnetic resonance, and chemical dynamics. A qualitative understanding of each ofthese field is important for an understanding of molecular organic photo- chemistry. ‘The intellectual structure of this field is inherently iterdisciphi equicesapractitionerto seek a commonality and integration ofthe ‘of many scientific disciplines. Such a process presents a challenge tothe student. To student who stars to lean a scientific subject, theories may appear tobe based on sisparate anc seemingly conflicting concepts and laws, such as the theory of waves ‘and the theory of particles, Molecular organic photochemistry must integrate theories4 Chapter 1 Motecuta Photochomisty of Organic Compounds: An Overview Com deen Gk. In his ext, the reuired inegrton of thas amd cones is whioved by providing a vituaaton othe molecular sutres, nergt, ened Aymmics involved in molecular ogi photochemical eatin (Other otatins for dying orgmie molelarphtechesry oe foun importance in modern ecologies, n molecule an chemi blog, medal applications, alin solar energy sous. For example ecules oi pte ‘hem provides understanding othe chan of phtosyntens the ands inenal process by which naire hamesesthe u's energy by the absorption sl photons fo rede food an every for out plane: Photsyaesi initiated bya Dray photochemical proces involving an lc anser action (Chaper Visor, ou most impart sense or obaring and ering in extra Wo ggeed by a remarkably simple primary procs of lets some, which tggersncacne of physiological evens al eal inthe seston of son nde we Dating te Ine 1900, he advent of ase eenology evolu the el tlecorimunicaonsby aking i paseo tarot information using ight (ough thas ber), raher tan electrons (rough metal wis). New technologies, terme Photonics enply light perform asks ht er origillyrlegted tothe doin of electronica, Photocenisty Is als taining an increatingly ior role fhe bel soon, cing ome Karns ef ance Glregh potters) tpling ‘ste, ad pestering mirosrery sig ler ter inpontan pplicson of photociemisy inde te we of ptliiogapy to manfactre compat his tnd photopolymer o pode proctiv somtings fora vat of high ae ati sah as pial es One ofthe "oly gas” of pts the *R in Scheme 1.1) and to deseribe the dynamies of the overall pathways from electronically excited states to products {ie.,"R Pin Scheme 1.1). Organic chemists are accustomed to analyzing ground state, thermally induced reactions of R in terms of molecular structure, molecular energetics, and molecular dynamics, We show that the femiliar molecular structoral theory of organie chemistry provides an effective and powerful starting point for derstanding mechanistic organic photochemistry. However, we have (0 make some {important modifications to the theary of ground-state reactions as we proceed. We ‘need to develop a theory of light and ofthe interaction of light with molecules where the usual strctural theory of organic chemistry is eplaced by a theory of interact ing waves, and where the classial continuum of states and energies is replaced by ‘quantized states and quantized energies. Consequently, we shall seck to understand sand visualize the paradigms of wave and quantam mechanies, which have evolved ‘san authoritative and powerfil means for understanding all structural and dynamic aspects of molecular organic photochemistry. ‘In order to understand molecular organic photochemistry, in addition tothe far {ae chemical representaions involving molecular structure and dynamics, we must develop an understanding ofthe concepts of electron spins, electromagnetic radiation, ‘and photons. The latter concepts awe desribed quantitatively and most effectively by the mathematics of wave and quantom mechanics. However, this text is directed at students who co not possess the mathematical background necessary for a quantita- tive computation of molecular propeties through quantum mechanies. Instead, we show that there are classical representations that are readily visualizable and capture the spirit and essence of most ofthe critical features of quantum mechanics that are ‘needed to understand moleeular organic photochemistry. These visualizabe classical representations will provide the student witha queaun intuition for an understanding ‘of the qualitative details ofthe pathways given in Scheme 1.1. For those who plan 106 Chapter 1 Molecuta Photochemistry o! Organic Compounds: An Overview ‘proceed more deeply into dhe mathematics of quantum mechanics, we hope tha the pictorial presentations will provide a useful framework fo the more quantitative mathematical aspets. To delve as deeply into the mathematteal aspect as desired, tho intrested and abe student ean proceed to standard textbooks and references on «quantum mechanics? 1.5 Scientific Paradigms of Molecular Organic Photochemistry CConssnsus exists among sient on how to pefou research and how to describe experimental obseevatons when authoritative scent paradigms exist hat provide a accepted process on how to dal wth important questions such as What ae the fndamentl entities that exist in the universe, and what ace their properties? and What.are the legitimate theoretical concepts and experimental tools tht ae requned to understand and to measute the properties ofthe eaites that exist? Authoritative paadigms allow the pracicing seiens to perform everyday research and enable a studet tobe readily initiated into a mature fed of science by studying, earning, and mastering the paradigms of the fel. ‘Now, we examine briefly the concept of scientific paradigms and How it relates tothe development ofa paradigm for molecular organic photochemistry. The simple paradigm of modem molecular photochemistry shown in Scheme 1 helps answer {he question What ae the Fundamental entities tat exist along a photochencal ‘¢ photophysical pathway? We wall also answer questions, such as What are the steutual, energetic, and dynamic properties ofthe entities showa in Scheme 1.1? and What are the legitimate theocetical concepts and experimental tools that are required t0 understand and to measure the propetes of these entities? We use the ‘wordparaigin” throughout the text because ois importance in science. We digress bretly nor to describe how the word has evolved in the scientific community In a book: enliled The Structure of Scenic Revolutions: Thomas Kuba, @ plilosopherof science, defined scent paradigm asa complex se of intellectual and experimental structures consisting of assumptions, concepts, steatogies, meth os, and techniques that provide a famework for performing sien research in 8 field and for organizing and interpreting observable phenomena ofthe universe in systematic and organized manner. Aceording to Kuba, the accepted paradigm of «field provide he authority to which scientists appeal in deciding othe course of everyday, nore scent activities and in recognizing expected result, exceptional results, and likely errors o artfuts. A scientific paraigan sets the expectations and P? For any reaction pathway 10 be possible, molecules (and their vibrational and spin substectures) must obey all four Section 1.8. Paradigms as Guidos ofthe conservation laws of chemical eactions: (I) the conservation of energy. (2) the conservation of momentum (linear and angular), (3) the conservation of mass (the rnumber and kinds of atoms), and (4) the conservation of charge. As we shall see (Chapier 8), these conservation laws place considerable restrictions on the number cof a priori possible stcuctares(*R, I, “I, P,*P, and F) and « priori possible pathways (Gebteme 1.1) that a photochemical reaction can follow. Only the se of structures and ‘pathways that obeys te canservaion lass is considered possible and all others are ruled out, absolutely, with no exceptions! However, even wen the conservation laws are fully obeyed, the paradigm con- stains the actual numberof plausible pathways for a photochemical reaction by the consideration ofthe details of molecular structure and implied energies and reorg zation associated with stevetural ransformations. In addition, one needs to consider available interactions that couple structures, and avaiable mechanisms of momentum and energy exchange, These considerations lead to a set of “sclection rules” that in dicate the plausible (at some assumed lovel of approximation) reactions that should be considered from the inital set of possible reactions. ‘To move from the plausible to the probable, you must consider specific details ofthe structure and the available interactions, reorganization energy, and time scales available to the plausible structures. These considerations determine the kinetics (oe rates) of each ofthe steps in Scheme I. ARer eliminating pathways based on Kinetic considerations, the remaining (much smaller) set of plavsible pathways, which occur atthe fastest rates is considered tobe the ser of most probable reaction pathways of the plausible processes—that is, those hat proceed at te fastest rates will win the race fiom *R to P and are therefore the most probable. We present paradigms that show howto generate selection rules fr plausible ses of pathwaysby employing structures, ‘ecrgetics,anditeractions that cause transitionsbetween structures to decide whether 1 pathway is possible, plausible, or probable. We also describe the experimentat ‘nd computational methods available to photochemists to experimentally “prove ‘which of the probable pathways is actually the one that occurs under a given set of conditions. Tnattemptingto understand an overall photochemical transformation, ++» P, it is very useful first to list all of the plausible parlasays that ate available to *R after the absorption of a photon by R (eg, from Scheme 1.1, the formation of 1, the passage through a funnel For the formation of “or *P) and then to qualitatively predict, based on selection rules described in Section 4.13, the relative rates of the plausible pathway(s to Pcompared tothe rate ofall other plausible pathwaysavailable oR that do not lend to P. Predicting an observed or most probable pathway of a photochemical reaction under a given set of conditions requires the ability to use the paradigm of molecular organic photochemistry shown in Scheme 1.1 to make informed judgments based on a knowledge of kaown, measured rates, exemplars, or theoretically estimated rates based on structure, interactions, energy, and dynamics fora given set of conultions. ‘The goal ofthis textisto teach, and forthe student to lear, the global and everyday working paradigms that relate, from cradle to grave, the structure, energetics, and10 Chapter 1 Molecular Photochemistry of Organle Compounds: An Overview ‘dynamics of molecules and photons to photochemical transformations, such as the ‘ovetall photochemical process R + —> P and the everall photophysical process Rt hv > R, 1.9 Some Important Questions that Will Be Answered by the Paradigms of Molecular Organic Photochemistry Now, let us consider in detail one ofthe possible paths of the global paraigm given in Scheme 1.1, the *R-> I> P sequence, which involves the following steps: 1. The absonption of a photon (lw) by a re clecteonically excited state (*R), 2. The primary photochemical reaction ofthe electronically excited state ("R) to produce a thermally equilibrated ground-state reactive intermediate (1. 3. The thermally induced reaction of Uo produce the observed products) (P). nt molecule (R) to produce an “The paradigm of Scheme 1.1 suggests that aphotochemnist should always ask and aempt to answer a number of standard questions concerning the details of an over photochemical reaction, R-+-hv -> P. For example, 1, How do we visualize a photon interacting with the electro absorption ofa photon to produce *R, and how does this interaction of a photon. and the electtons of R relate to theoretical and experimental quantities, such as extinction coeficients, radiative lifetimes, and radiative efficiencies? What are the possible and plausible structures, energetics, and dynamics available to “R and I that occur along the reaction pathway from *R > P? 3. What ate the possible and plausible sets of primary photochemical processes corresponding to the "R—> I process? 4. Whatare the legitimate theoretical approaches, eyperimental design strategies, experimental techniques, and computational strategies for experimentally “observing” or validating the occurrence of the species *R and I that are postulated to occur along the reaction pathway from “R > P? 5. Whats the most probable pathway from *R > 1? 6. How is the most probable pathway determined by the competing kinetic pathways for the photophysies and photochemistry of *R? 7. What are the absolute rates (cate constants) at which each elementary step ‘occurs along the reaction pathway from "R -> P? 8. What sorts of structures, energecs, and dynannies correspond to *R and Tin \ypical organic photoreactions? Questions such as these ancl many more that are implicitly posed by the paradigm fof Scheme 1.1 (and its elaborations) can be handled by establishing a more detailed working paradigm and by referencing exemplars thal serve as benchmarks for the aualysis of photochemical reactions Seaton 1.10 From a Global Paradigm to the Everyday Working Paradigm 1.40 From a Global Paradignn to the Everyday Working Paradigin In solving normal scientific puzzles, we save a great deal of time by employing an “everyday working paradigay” that is based on considerable experience or precedent ‘and that is found to be generally applicable to a wide range of commonly encoun {ered situations, This shorteu of using @ working paradigm is a sort of mechanistic “Occam's razor" relieving the photochemist from always starting from seratch and ‘examining a lage number of hypothetically plausible, but historically improbable sit uations each time a photochemical eaction is analyzed, an experimentis designed, or ‘theoretical point is discussed. The paradigm discourages the scientist from wasting ‘ime by considering theoretical or expesimental situations that are expected to be out- side the paradigm. In our study of molecular organic photochemistry, we shall always star with Scheme 1.1 asthe global paradigm and determine how we can continuously claborate it into an ever more specific everyday working paradigm for molecular or _ganie photochemisty. A very effective method for refining Scheme!.1 isthe appeal to exemplars ‘As mentioned in Section 1.6, students of organic chemistry are familiar with the effectiveness ofthe exemplar approach through the study of functional groups, where 1 funetional group is an alom or group of atoms that possess qualitatively sil reactivities, spectroscopic propeties, and physical propesties that are independent of the molecule in which the functional group is found, ‘Coupling the functional group approach with exemplars from molecular orbital (QO) theory provides a powerful means of predicting chemical reactivity ataquaita ‘ive level and willbe used extensively in this text to advance an understanding ofthe photochemistry of exemplar systems. Weshow that, to good starting approximation, having an understanding of the photochemistry ofthe common functional groups of ‘organic chemistry (eatbony, olefinic, enone, aromatic compounds, etc.) means the ‘working paradigm nceds only to consider two things: (1) the electron configuratio of two MOs [the highest occupied molecular orbital (HOMO), abbreviated as HO, and the lowest unoccupied molecular orbital (LUMO), abbreviated as LU} and (2) the clecton spin configurations ofthe electrons in the HO and LU for the Key structures Ge R,*R, and P) shown in Scheme 1-1. ‘Scheme 1.2, an elaboration of Scheme I, inchudes the energy levels of the HO ‘and LU of R, *R, I, and Pas a working paradigm for the examination of molecular ‘ganic photochemical reactions tht proceed through the path R hv > *R—> 1» Scheme 1.2 displays qualitatively the energies of the HO and LU, anc at this level, clecton spin is not explicily considered. The energies ofthe HO and LU for R,*R, and P are assumed to be far apart (\ypically > 40 keal mol”), whereas the energies of the HO and LU molecular orbitals for Lare assumed to be very similar and may often be approsimated as nonbonding (NB) orbitals. It is assumned in the working paradigm of Scheme 1,2 that all ofthe remaining electrons that are not showa inthis scheme are spin paired (according to the aufbau and Pauli exclusion principles) in orbitals oF lower energy and ace of secondary importance in determining the course of "2 Chapter 1 Molecular Photochemisty of Organic Compounds: An Ouerviowr a —™ np ——+ 1 ——+Pe w — Hey ae Ho ca wor oyu! (9,7 83" tof ‘Schane 1.2 The global paradigm of organic photochemical reactions depleying ttt configurations of RR, 1, and P {he photochemical and photophysical processes (because these lower ace dificult to perturb, even in photochemical processes). ‘The starting point for the analysis of a photochemical or photophysical process is the assignment ofthe electronic nature of the HO and LU for Rand *R. This mounts to assigning a speci electron configuration to R(HO)? and *R(HOM(LU). “The reactive intermediate is genealy a species possessing vo nonbonding oxitals that are produced by the primary photochemical process *R -> K(NB)'(NB)!. There are no HO or LU of very different energies in the later case, bat instead there are two NB orbitals of similar energy. Thus, the chemisty of Iwill be determined by the «electronic configuration of to electrons in two NB orbitals and, as we shall seein ‘Section 1-1, by the spin configuration of the two electrons, 00). When the two NB orbitals are located mainly on eatbon atoms, the lowest- nergy orbital configuration of Feorresponds to one electron in each NB oxbital fi, T¢NB)'QNB)}, thus producing a radical pair (RP) or biradical (BR). (The terms "bi. radical” and “cicadicat” are sometimes used interchangeably inthe photochemical iterate, but we use the term “bicadical” solely forthe situation in which two NB cbitals each contain one electron and both NB orbitals are contained inthe same ‘molecular structure, We use the symbol D to mean a more general “radical” species that could be a RP, BR, or some related structure. The definition of a dicad- icaloid is discussed in detail in Chapt 6) In soe eases, when the energies of the NB orbitals are significantly different, the reactive intexmedate T may possess an electron configuration that places both leetrons inthe lower-energy orbital a situation that requires the two electrons tobe spin paired. Such electronic configurations eorespond to species called zwitterions, 2(NBY?, which for simplicity we ae ignoring al this poi Ina cases the orbitals assigned to the HO and LLU wil be simple one-electron ‘orbitals that are familiar othe student from courses in oxganic and physical chemist nergy electrons ‘Section 1.10 From a Global Paradigm to the Evoryday Working Paradigm 13 Jin this approxinvation, moreover, we ignore electron-electron repulsion that would lead to different energies of the HO and LU in R and *R. This approximation is discussed in more detail in Chapter 2 and is employed throughout the text. “The working paradigm of Scheme 1.2 suggests a number of questions that need to bbe answered when studying or analyzing any organic photochemical eacto 1. What are the electronic charscteristies of the HO and LLU involved in the + hw => °R process? 2. What isthe electonic configuration of *R (Le, the erbital occupancy of the HO and LU)? 3. What ace the plausible primary photochemical and photophysical processes \ypical of *R based on its election configuration (HO)"(LU)"? 4. What are the electronic natures of the NB orbitals of 17 5. What are the plausible secondary thermal reactions of T that lead (0 P? Scheme 1.2 requires one more level of structural elaboration before it ean be ‘employed as an everyday working paradigm. (For simplicity, at this stage, we are ignoring both the *R > F processes and the “R > "T processes.) The nature of the funnel (F) will be considered in detail in Chapter 6. This final level of detail includes not only the electronic configurations of *R and I but also the electronic spin configurations of °R and I, a shown in Scheme 1.3. Now, we consider the role ‘of spin in photochemical reaction ofthe ype *R > I> P. ty o ate o a—™ si ——_>P @ aM tae op so) B2, 1) +p we — @ soe WOH sy eva RES) — "RS,) FR) — %1O) — (0) PS) ‘Sonam 1.3 Exemplar paradigm for an organic photochemical reaction tha proceeds Aheough a pet tat1“ CChapter 1 Molecular Photochomisty of Organle Compounds: An Qvervewr 1.41 Singlet States, Triplet States, Diracdicals, and Zwitterions: Key Structures Along a Photochernical Pathway from °R to P Scheme 1.3 deseribes an elaboration ofthe orbital and spin sttural detail forthe exemplar photochemical reaction R + > *R > 1(D) > P Fst, we consider the laboraton of the oxi description of the species along the reaction pal), then we consider an elaboration of the spn desription ofthe species along the rezeion path (©). ‘The electronic configurations of the ground states of R and P are generally (HO}CLU)’ for ordinary organi molecules. According to the Paul exclusion prin- ciple, the spins of two electrons inthe same orbital must be pated (he spins will be symbolized as 4, termed “antparale spins" nd eonespond to & single si configuration ora singlet state). The electronic configuration of *R and I, both of typically possess one electron in cach of the tvo key orbitals (HO and LU ot the two NB orbitals shown in Scheme 1.34, are wot equied by the Pauli exclusion principle to be spin pared so the two key electrons inthe hal filled orbitals ean be cither paid (1, singlet states) or unpaired (symbolized as fan refereed to a8 “parallel spins,” coresponding o «tiple spn configuration oa tpt state) “The single states of a melecae ae given the symbol 5, where the substi ranks the enorgy of the singlet stat. The subscript Os reserved forthe towestenciay lecttnic ground state, which isalvaysa singlet slate (.,S) fr ordinary organic amoleutes. The fist exitedsnglet states, the seconencite singlet states, ne soon, When *R (or possesses two orbitlly unpaired cletrons andthe electron spins ave spin unpaved CF), he structure is termed a per state and labeled T,, where te subscript ranks the energy of the wile state (Sines the sbserpt Dis reserved for the fowest-energy electronic ground stat (i, Sq), = 2. for trp states, andthe lowest energy tiplet state is] The terms “singlet” and “ple” originate from the magnetic properties of election spins (Chapter 2. In general, R and P represent the singlet ground slates of erganie molecules, so they are given the symbols R(Sq) andl P(S,). I the elections axe spin paired (Fin “R this isa singlet excited state and iis labeled, where the subscript indicates that the state is the fst excited singlet stat [i.e "R(S) in Scheme 1.3}. Ifthe election spins ae parallel (14) in “R, this isa tiplt excited slate and tis fbeledT, where the subscript indicates that the state isthe fst Wile excited state fie, *RCH) in Scheme 1.3} Likewise, the reactive intermediate I with one electron in each of two orbitals of similar energy (@g, 090 noabonding oxitals) may be ithe a singlet "(H) or etplet ICP. We use the symbol D (lor diradicst) asa generat abel fora wermediate (I) produced from *R that possesses two half filled oxbitals (eypicaly both nonbonding) of comparable energy. The symbo D represents both RE species in which one radical center is Focated on each of two molecular fraginens, and BR, species in which the two radical centers ae located en a single molecelay structure. Ths, the symbol 1(D) refers to a reactive intermediate tha possesses reactive Section 111 Singlet States, Tiplot Stats, Biadioals, and Zwiterons diadical character and for which the two half-filled orbitals are of similar energy. “The UD) species dill fiom *R, because *R species possess two half-filed orbitals tat ace of ery different energies. This distinction wil be of particular imporiance ‘when we consider the role of electton-leetron interaetion in changing the energies of orbitals from the values for one-eleeton orbitals ‘The symbols 'ICD) and 3(D) represent singlet and triplet diradcal intermediates, respectively. The superscript indicates the spin state ofthe intermediate, and the D reans the intermediate possesses two electrons in halffilled orbitals. Then, it fol lows thatthe symbols (RP) ane! M(RP) represent singlet and riplet radical pais, respectively, and the symbols 1(BR) and °1(BR) represent singlet and triplet ira cals, respectively. Lis ima singlet state, itis also possible forthe two electrons to be in one NB ‘xbita, and for no electrons tobe in the other, that i, ONBY"(NB). Such a species isreferred to a8 a cwitterion and given the symbol I(Z). The IZ) species ae involved in the "+ (Z) and the "8 - F steps of photoresetions involving certain singlet slates, whereas D species arealvaysinolvedinthe *R ~>"I(D) stepof photochemical reaelions involving photochemical processes initiated in R, The rules for D or Z formation and the chemical properties ofthese species ave deseribed in Chapier 6, Scheme 1.3 represents a working exemplar paradigm forall photochemical reac- tions of organi molecules that proceed through triplet excited state, *R(T)). Forany given reaction, R may be a carbonyl, an olefinic, an enone, an aromatic compound, ‘rs0 on. We need to know the nature ofthe HO and LU of each ofthese structures to Aeduce the eleewonie configuration of *R. Given the electonie configuation of *R, swe can generat “selection rules” forthe plausible pvinary photochemical rections °R 1. Predicting and understanding photochemical reactions requires a Knowledge ofthe structures f the entities shown in Scheme 1.3, namely, Rp), "RS, RCTs 34, 4, aud PCS), and of the probabilities ofthe transitions between the sinactures connected by the pathyeays shown in Scheme 1.3(€) In Chapter 6, we see that when the electronic configuration of Tis HO =n (ie, a nonbonding MO) and LU = 1 Gc. an antibonding MO), which isthe eae for acetone, benzophenone, and many other ketones, there is only a small set of primary photochemical processes ofthe type °R(T}) ->*1(D) that ate pheusibl. The important tole of electron spin reas its head in the overall reaction because (Scheme 1.3) the reactive intermediate *(D) must be comerted toa singlet intermediate, "(D), before the final product PS), which is a singlet stat, can be formed. How do the ISC processes *R(So) —> *R(T)) and °10D) +40), which require a ehange in electron spin, occur? A useful vector representation ofelectcon spn is ‘presented in Chapter 2to describe how election spin operates tocontl the steps that iterconvert singlets and triplets In Chapters 3 and 6, this vectorial representation ‘of electron spin i used to answer questions pertaining tothe interconversion of spin states, Now that we have introduce the important global and exemplar paradigms for analyzing organic photochemical reactions, we ean develop the state energy diagram, which makes it possible to wse and manipulate the working and exemplar pai 16CChaptor1 Molecular Photochemisty of ganic Compounds: An Overview (@) Norrish Type I reaction: lO) = ractcal pai, (AP) Dea ake ca Kod K 7 cal“ ead Sw AS i, feo, ip HP. ip, (6) Norsh Type Il reaction: [O) = braical, NBR) Galle Gls Calls — ° ce be ce te, (Sor Ae. bay — onbcat i, my ony < a Tn He. om He. pe Figure 1.1 (a) Ancxample of primary photochemical R > (RP) proces, the "Type secleavage of ketones. (0) An example of a primary photochemical “R -> KBR) process, the “Type UI intramolecalar hydrogen abstaction of ketones with alkyl side ens [Figure 1.1 presents two concrete exemplars of R -> I(D) primary photochemical processes. In the first example, the Noresh Type I reaction, *R. undergoes an a- cleavage of the C=C bond of the C=O function to produe a radical pair, (RP). In the second example, the Norrish Type If reaction, *R undergoes an intramolecular Inydrogen abstraction o produce a biraiesl, (BR), These two types of *R => (D) ‘primary photochemical processes are very common are provide excellent exernplars {or the analysis of the photochemical primary processes of a wide range of organie molecules, 41.12 State Energy Diagrams: El tronic and Spin Isomers: According to Scheme 1.3, our exemplar paradigm of organic photochemistry, there are three important molecular states, (Sp), *R(S,), and °R(T}), that must always be considered when starting an analysis ofa photochemical reaction involving organic molecules. A state energy diagram (Schenne 1.4) provides a compact working exem- plar for displaying the relative energies and keeping track of the ground state (S,), the lowest-energy excited singlet state ($j), and the lowest-energy triplet state (T}) of an cotganic molecule (where Es is the energy of S, and Zs the energy of T)). The elec- ‘ionic configurations of the SS}, and T states are also shown. Higher energy singlet Sates (S2, $3, te.) and higherenergy triplet states (Tp, Ts ete) can also be included 5 desired, but need not be explicitly included in the working state diagram, because ‘experience has shown that excitation ofthese higher-energy excited states generally vesuls in deactivation 1o Sy and'T faster than any other measurable process (Kasha's Section 1.12. State Enexgy Dlagiams: Electonic and Spla isomers St enagy ‘plat eoway Saji enon ‘pet reacion Irae aosing fd i ‘ip pin coigwaton ‘Single conuration © @ we WO tw Ho Srejt-sijt espn 5) Sa ist ebeoron uence | Phogphaescance tetera eoevrion ———d | ntarystom essing Schone 14 The sta energy diagram is Fundamental poradign of mavdem meleculor photochemistry. The intersystem-crossng ete constants and kare sometimes referred. asks rule, Chapter 4). In state energy diagram, the y-(vertcal) coordinate represents the potential energy (PE) of the system. The s-(horizontal) coordinate has no physical ‘meaning (i is nora reaction coordinate or potemial energy surface). The lines rep. resenting the state energies of Sy and T, are displaced for convenience andl to avoid congestion. Thus, a state energy diagram shows the ranking ofthe energies of the Sy, "7, and S; states and is most useful if actual values ofthese energies can be associated ‘vith the T, an Sy states, How the enezgies ofS and T, are detormined experimentally is described in Chapter 4. ‘State energy diagrams are sometimes referred to as Jablonski diay of Aleksander Jablonski, a Polish physicist who used a schematic post relative postions ofthe electronic and vibrational levels of R and *R without any attempt to indicate the relative nuclear geometsies. For simplicity, vibrational levels are omitted in this introduction tostate energy diagrams. Vibrational levels, which are important in determining therates of photophysical processes, are introduce into state energy diagrams in Chapter 2. Tn state encegy diagrams, iis assumed that the equilibrium nuclear geom Rand "8 are similarand that these geometries represent minima of Rand "R. Since all, of 1"