CHM 325 - 2020

INTRODUCTION TO MATERIALS CHEMISTRY

K2Pt(CN)4Br0.3.2H2O

Br
K
N
C
Pt

SYNTHETIC ELECTRICAL, OPTICAL AND MAGETIC MATERIALS BUILT OF

ORGANIZED ARRAYS OF ORGANIC, INORGANIC, ORGANOMETALLIC,
COORDINATION COMPOUNDS AND POLYMERS
1
 5 KEY DEVELOPMENTS IN SOLID STATE
MATERIALS CHEMISTRY
1. SOLID STATE MATERIALS SYNTHESIS

2. X-RAY DIFFRACTION STRUCTURE OF SOLIDS

3. ELECTRONIC BAND PROPERTIES OF SOLIDS

4. TYPE, POPULATION, FUNCTION OF DEFECTS IN SOLIDS

5. ENABLED UTILITY OF SOLIDS IN ADVANCED TECHNOLOGIES

2
 thinking
materials
utility

function

3
FIVE COMMANDMENTS OF SOLID
STATE MATERIALS CHEMISTRY
1. Synthesis – bulk and surface
composition, structure, size, shape,
defects, assembly

4
FIVE COMMANDMENTS OF SOLID
STATE MATERIALS CHEMISTRY
2. Structure – all length scales,
nanometers to microns and beyond,
crystalline or glassy, morphology
(shape, form), poly-morphology (same
composition different structure) and
texture (polycrystalline, single crystal,
thin film, nanocrystalline)

5
FIVE COMMANDMENTS OF SOLID
STATE MATERIALS CHEMISTRY
3. Property – metal, semiconductor, insulator,
superconductor, superionic, supercapacitor,
paramagnet, ferromagnetic, antiferromagnet,
ferroelectric, paraelectric, piezoelectric,
electrochromic, thermochromic, barachromic,
thermoelectric, phosphor, nonlinear optic, optical
gain, photorefractive, photoconductive,
photocatalytic, electrocatalytic, magnetooptical,
magnetoresistant

6
FIVE COMMANDMENTS OF SOLID
STATE MATERIALS CHEMISTRY
4. Function – ionic and/or electrical
conductor, light emission, color change,
electrical or optical switch,
chemistry/light/heat to electricity or
fuels, water softener

7
FIVE COMMANDMENTS OF SOLID
STATE MATERIALS CHEMISTRY
5. Utility – battery, solar cell, solar fuels,
fuel cell, chemical sensor, color display,
data storage, transistor, bio-
diagnostics, solid refrigeration, LED,
laser, catalyst, gas separation, storage,
release, water softener

8
9
 Synthetic
strategies for
making a
material

Potential uses
for a material Materials
based on its structure
function
Chemistry Cycle for
Asking How to
Create Novel
Materials, Devices
and Processes
Synthetic
Relation of control of
properties to material size,
function shape,
surface
Relation of
materials
structure and
defects to
properties

10
 Chem 325H1
Lecture 0
Materials Diagnostics
CHM 325H
INTRODUCTION TO MATERIALS CHEMISTRY
• Instructor: Dr. Paul Duchesne
• email: paul.duchesne@utoronto.ca
• Recommended Texts: L. Smart, E. Moore: Solid State Chemistry,
P. A. Cox: The Electronic Structure and Chemistry of Solids
• Web Notes: Quercus
• Teaching Schedule: Six Two-hour Thursday 5-7 pm Lectures a
Week

• Test Schedule and Marks: Inorganic Mid-Term Test 25%

(Date TBD , 7-8 pm LM 158), Combined Final Exam 50%

12
CHM 325H
INTRODUCTION TO MATERIALS CHEMISTRY

• Traditional metals and semiconductors are normally

associated with solid-state materials like Na, Ag, Pt and Si,
GaAs, CdSe
• Their structure–property relations are described within the
framework of Bloch-Wilson electronic band theory and
Schottky-Frenkel defect theory

13
 CHM 325H
INTRODUCTION TO MATERIALS CHEMISTRY
• This course is about non-traditional metals and semiconductors
• The building units are not Ag or Si atoms organized in an extended
periodic 3-D network structure
• Instead they are composed of regular arrangements of organic
and inorganic molecules, coordination/organometallic compounds,
clusters, or polymer building blocks, which can function as novel
kinds of metals and semiconductors.
14
 CHM 325H
INTRODUCTION TO MATERIALS CHEMISTRY
• The synthesis of various representative members of this class of
non-traditional materials will be described
• Relations between their structure and bonding, properties and
function will be examined
• Their utility in application areas like solar cells and batteries,
light-emitting diodes and transistors, smart fabrics, sensors and
digital displays will be explored

15
 COURSE CONTENT
• Inorganic stackers
• M(dpg)2, M(Pc)
• Krogmann’s salt, K2Pt(CN)4
• Mixed valence, [Pt(am)4][Pt(am)4Cl2]Cl4
• Inorganic & organic conjugated polymers
• (SN)x and (CH)x

• Organic systems
• Organic stackers: (TTF)(TCNQ), (TMTSF)2ClO4
• Organic conjugated polymers: PT, PA, PP, PPV

16
 MILESTONES IN SYNTHETIC ELECTRICAL CONDUCTORS
• Henry Letheby discovered the earliest
known organic conductive material in 1862

• Made by anodic oxidation of aniline in

sulfuric acid

• Produced a partly conductive material much

later identified as poly-aniline (PANI)

17
https://upload.wikimedia.org/wikipedia/commons/thumb/f/f6/Polyaniline_structure.svg/1920px-Polyaniline_structure.svg.png
MILESTONES IN SYNTHETIC ELECTRICAL CONDUCTORS
Perylene
1911 Suggestion organic solids can be electrical conductors

H.K. Onnes discover Hg is a superconductor

1954 Bromine salt of perylene show electrical conductivity

1957 Bardeen, Cooper, Schrieffer (BCS) theory of TCNQ

superconductivity based on e--ph-e- coupling

1962 Synthesis of tetracyanoquinodimethane (TCNQ)

1964 Little suggests RT superconductivity is possible

18
 MILESTONES IN SYNTHETIC ELECTRICAL CONDUCTORS

1968 Krogmann’s salt (K2Pt(CN)4): inorganic

coordination compound – 1D electrical
conductor with Br2
1970 Synthesis of tetrathiafulvalene (TTF)

1973 TTF-TCNQ first organic metal

shows Metal  Non-metal transition at 54 K

1974 Polythiazyl (SN)x: first inorganic polymer,

found to be an electrical conductor and
superconducting at 0.3 K

19
https://upload.wikimedia.org/wikipedia/commons/f/f5/Polythiazyl-2D-dimensions.png
 MILESTONES IN SYNTHETIC ELECTRICAL CONDUCTORS
1977 SNBr0.4 – doped polythiazyl, superconducts at 0.36 K
Shirakawa found 1000x increase in electrical conductivity
of polyacetylene ((CH)x) on oxidative and reductive
doping

1979 TMTSF-DMTCNQ donor-acceptor material synthesized,

s = 105 -1 cm-1 at 10 kbar and 1K
Bechgaard salt ((TMTSF)2X, where is avmonovalent
anion), superconducting under pressure at 1 K

1980 (TMTSF)2ClO4 superconductivity ambient pressure at 1 K

20
 MILESTONES IN SYNTHETIC ELECTRICAL CONDUCTORS
1983 (BEDT-TTF)2ReO4: first sulfur-based organic
superconductor under pressure at 2 K

Ni(Pc)I: non-TTF based molecular metal

that remains metallic at low T

1984 b-(BETD-TTF)2X, where X is a complex anion:

superconductivity at ambient pressure and 10–20 K
BETD-TTF = bis(ethylenedithio)tetrathiafulvalene

1985 C60 synthesis

1986 LaxBa1-xCuO4-d: Bednorz and Muller discover high TC

ceramic oxide Perovskite-based superconductors
21
https://upload.wikimedia.org/wikipedia/commons/thumb/9/9b/MultistepFullereneSynthesisScott2002.png/800px-MultistepFullereneSynthesisScott2002.png
 MILESTONES IN SYNTHETIC ELECTRICAL
CONDUCTORS
1990 Scale-up of C60 synthesis
Superconductivity in MxM’3-xC60
1991 S. Iijima discovers single and Me Me
multi-wall carbon nanotubes Si

Me
Fe Si Fe
1991 polyferrocenylsilanes (PFSs) reported by Manners
Me

(UofT): redox active, magnetic p-type hopping n

semiconductors Polyferrocenylsilane (PFS )

amber, film-forming polymer

1993 TC=133 K in HgBaCaCuO
Mw = 520,000, Mn = 340,000
1994 TC=160 K in HgBaCaCuO under pressure
1998 VLS synthesis of diameter- and length-controlled
22
semiconductor nanowires by Lieber, Yang
Bi2S3 – 1.6 nm diameter is a size that bridges the fuzzy regime
between molecular and nanoscopic objects, and rigid and
flexible nanowires/polymers

The dawn of something new and exciting in materials chemistry

and nanochemistry, emerging fields that never tire of reinventing
themselves.

23
L Cademartiri and GA Ozin, Advanced Materials 2008, 21(9), 1013.
 Graphene - Single Sheet Graphite
Andre Geim and Konstantin Novoselov 2010 Nobel Prize

24
Image credit: Egorov Artem / Shutterstock
Single Sheet Metal
Dichalcogenides, MS2

Exfoliation or
direct synthesis

Ultrathin
semiconductors

25
Black Phosphorous
Chemical Exfoliation to Single Sheets

26
Exfoliation of Hexagonal BN - Single
Sheet BN – Excellent Nano-Insulator

27
Reassembly of Single Sheet Nanomaterials Creates
Designer Layered Nanocomposites

28
 2D Nanosheet Device Revolution

An ultra-thin and flexible 2D MOSFET transistor built on a silicon wafer (Si/SiO2)

uses graphene (black spheres) for the source (S), drain (D), and gate (G)
electrodes; molybdenum disulfide (yellow and green spheres, MoS2) for the
semiconductor layer; and hexagonal boron nitride (pink and blue spheres, h-BN) as
the insulator.
29
CONDUCTIVITY OF POLYMERS AND MATERIALS

Range of 1024 from good insulator to good conductor

(S cm-1)

30
 BLOCH-WILSON CLASSIFICATION OF CONVENTIONAL
INSULATORS, SEMICONDUCTORS, METALS

Ef Dopant
CB Ef Energy
Ef
Eg States
VB

CONDUCTOR INSULATOR SEMICONDUCTOR

• partially filled CB • fully filled VB • fully filled VB
• (e-)s free to move • large Eg • small Eg(band-gap)
• Ef top of CB •Ef between VB-CB • thermal excitation to CB

31
THINKING ABOUT CONVENTIONAL
DOPED SEMICONDUCTORS

e e e
Ef
Eg Ef
Ef
h h h

intrinsic n-doped p-doped

semiconductor Excess electrons Excess holes
32
 DEFINING AND MEASURING
ELECTRICAL CONDUCTIVITY
I
1 𝐼 𝐿
L 𝜎= = · (Ω-1 cm-1)
ρ 𝑉 𝐴

Increases
For semiconductors:
−𝐸𝑔
with T 𝜎 𝑇 = 𝜎0 · 𝑒 2𝑘𝐵 𝑇
V
Decreases For metals:
with T 𝜌 𝑇 = 𝜌0 +bTγ
area (A)
• Single crystal vs. pressed powder with grain boundaries
• Four probe: constant current (I) – measure voltage drop (V)
• Hall or Seebeck effect measurement defines sign of e- or h+
carrier
33
https://upload.wikimedia.org/wikipedia/commons/8/84/Four-point.png
Useful Relations
Electronic Bandwidth (W) relation to Orbital Overlap (S),
Electron Mobility (me), Electron Effective Mass (m*)
E
𝑑𝐸
𝜇𝑒 ∝
𝑑𝑘
Wide band width
2 −1
𝑑 𝐸
𝑚∗ ∝
𝑑𝑘 2
EF
W
Narrow band width

EF
2π
𝑘=
-k k
𝜆
34
ELECTRONIC PROPERTIES OF SOLIDS
Some interesting and useful relations
• Wave vector k = 2/ (k is electron momentum in reciprocal space a.k.a “k-
space”)
• E = mc2 (Einstein)
• p = mc
• E = pc = h (Planck)
• p = h/c = h/ (de Broglie) – wave particle duality
• p = hk/2 thought of as electron momentum in reciprocal k space

1. 𝜇𝑒  dE/dk = electron mobility at EF

2. m*  (d2E/dk2)-1 = electron effective mass at EF
3. W = electronic bandwidth, good orbital overlap large bandwidth
4. Wider bands (larger W) mean larger slope: dE/dk and larger 𝝁e
5. Wider bands (larger W) mean larger curvature: d2E/dk2 and smaller m*
6. Smaller m* means higher electrical conductivity (s) 35
 Unconventional Metals and
Semiconductors Synthesized from:
Organic/Inorganic Molecules,
Organometallic Compounds,
Coordination Complexes and Polymers
1D SYNTHETIC ELECTRICAL CONDUCTORS
MOLECULAR STACKERS - BUILDING BLOCKS
Organic-Inorganic Macrocyclic 1D Conductors
H H
O O O O
R N N R N N
M M
R N N R N N
O O O O
H H

Glyoximate Complexes M2+= Fe, Co, Ni, Cu, Zn, Pt

Planar metal-organic macrocycles with conjugated double
bonds suggests formation of stackers and 1D conductivity
37
 H 1D SYNTHETIC ELECTRICAL
O HO
R NO HNO R CONDUCTORS
R NO HO
MO N HO R
R NM N H R
O O MOLECULAR STACKERS
R N
R N R
NM O N H OR
R ON R ONNM O RNHHO R BUILDING BLOCKS
R ONHR R ONN O RN O R
R OH
N O NH O R
N R OMNN R NH O R
Organic-Inorganic
M OO
R OHNR R O NM ORNHHOOR
N Macrocyclic 1D
R HN R N NN O RNNH OR R
M
R O N RO M N O R NH O R Conductors
R OH N R O NM
NN O R NH O R
R O HN R O MN O R NH O R
R O HN R O N M
N O R NH O R
R O HN R O NM
N O R NH O R
R O HN R O NM
N O R NH O R
R O HN R O N M
N O R NH O R
R O HN R O NM
N O R NH O R
R O HN R O N M
N O R NH O R
R O HN R O NM
N O R NH O R
R O HN R O N M
N O R NH O R
R O HN R O N M
N O R NH O R
R O HN R O N MNN O R NH O R
Pristine R O HN O M
N O R NH O R
R O HN R O N
R MNN O R N O R
R O HN O M
N R
macrocycle stack R O HN R O N
R NN RNN R R
M
R O HN O M N R
behaves as an R O HN O M
R O HN O M
N
N
R
R
insulator R O HN O N R
R O HN O N R
OH O
OH O 38
H
 SYNTHESIS OF METAL GLYOXIMATES
H
O O
O O
HO N N OH
MCl2 R N N R
H2N OH M
R R Hydroxylamine R R R N N R
1,2-diketone
O O
O
H
O H2
N
OH
+ 2 HCl
R R
Analogous
H reaction
H
with 2nd
Chelate effect drives
O O
N NH2OH complex formation
OH
molecule
R R
Lone pairs at N make
- H2O
bonds with empty M(II)
O N
OH d-orbitals
R R
39
 1D SYNTHETIC ELECTRICAL CONDUCTORS
MOLECULAR STACKERS - BUILDING BLOCKS
Organic-Inorganic Macrocyclic 1D Conductors

Phthalocyanine and Metal Phthalocyanine Complexes

40
 N
N
Metal Phthalocyanine
N
N
N
NN
N
N Molecular Wire
N
N M
N
M N NN
NN
N
N
N M
N
MN
N NN
NN
N
N
N
N MM
N
N
N
N NN
NN
NN
N
NN
N M
M
N
N
N
N NN
NN
NN
N M
NN
NM
N
N
N
N NN
NN
M
NN
N
MNN
N
N
N
N
N NN
NN
M
M
NN
N
NN
N
N
N
N
N NN
NN
MM
NN
N
NN
N
N
N
N
N NN
NN
MM
NN
N
NN
N
N
N
N
N NN
NN Pristine
M
M
NN
N
NN
N
N
N
N
N NN
MM
NN
N
NN
N
NN
N
N
N
N
macrocycle
N stack behaves
NN N
NN N
N
N
as an insulator
N

41
SYNTHESIS OF METAL PHTHALOCYANINES

CN 200 °C
MX 2 + 4
(Metal ion acts
CN
as template for
cyclization)
Phthalonitrile

Metallophthalocyanine (MPc)

42
CO-ASSEMBLY SYNTHESIS OF METAL
PHTHALOCYANINES – METAL TEMPLATE
DIRECTED

MX 2

Coordination  Electron redistribution  Cyclization

43
Materials Food for Thought
In the reaction shown on the previous slide,
explain the co-assembly chemistry of the
metal and organic building blocks clearly
showing the electron redistribution and bond
formation cyclization processes and decide on
the fate of the halide
 STACKING TYPES – STACKING INTERACTIONS
M M
M M
M M M
M M
M M

planar tilted offset

• bonding and non-covalent bonding (VdW) interactions

• crystal packing interactions M M M

M M M
• intra- vs. inter-stack interactions M M M
M M M
• - vs. M interactions (or both) M M M
Inter-stack interactions 1D  2D  3D 45
THINKING ABOUT STACKER CHARGE TRANSPORT
Pristine macrocycle stack behaves as an insulator

Partial oxidation (e.g., by I2) turns stack into an electrical conductor

Multiple possibilities for intra-molecular stacking interactions:

1. pz orbital overlap of C atoms of macrocycle
2. dz2 and pz orbital overlap of M ions z

1. 2. M

3. Both possibilities could also contribute simultaneously 46

 THINKING ABOUT STACKER CHARGE TRANSPORT
1. 2. M

Both possibilities could also contribute simultaneously.

• Experimental data with I2 oxidative doping suggests Form 1 is

predominant:
• Exchange of M2+ by H+ does not much affect the conductivity
• Evidence for oxidized macrocycle: radical cation EPR, NMR
• Oxidation state of metal ion remains unchanged (from XPS) 47
 THINKING ABOUT STACKER ELECTRONIC BANDS
most
Insulator M or SC anti-
bonding
orbitals

•••
[Ox]

1
most
bonding
n orbitals

• Ground state stack, full -electron orbital overlap creates -bands

• Doping by oxidation creates partially filled -band
• Metal vs. semiconductor nature depends on delocalized or localized charge carriers
• Interactions between stacks determines whether Metal-Non-metal transition occurs on cooling 48
TUNING THE DEGREE
OF FILLING
OF STACKER 
ELECTRONIC BANDS
THROUGH OXIDATIVE
OR REDUCTIVE
DOPING CONTROLS
THEIR ELECTRICAL
AND OPTICAL
PROPERTIES AND
EFFECT OF
TEMPERATURE!
49
Case History M(dpg)2
H
O O
R N N R
M M = Ni(II), Pd(II)
R N N R
O O
H
d8 square planar complex
R = phenyl C6H5
• extended  electron orbitals
50
 H
O O M(dpg)2
R N N R
• M = Ni(II), Pd(II)
M
R N N R • d8 sq. planar complex
O O • R = phenyl C6H5
H • extended  electron orbitals
Oxidation of M(dpg)2
• M(dpg)2 + 0.5 X2  M(dpg)2X (X = Br, I)
• Slow cooling hot o-C6H4Cl2 solution of M(dpg)2 with X2
• M = Pd  black shiny crystals
• M = Ni  golden olive green crystals
• Elemental analysis: M(dpg)2X1.0

• Pd(III) and Ni(III) metal center? Oxidation of ligand? Both???

51
(a) RAMAN - VIBRATIONAL
CHARACTERIZATION OF
OXIDIZED M(dpg)2I STACK
(b) Ni I2
(I-I) fingerprint low frequency
stretching modes

(c) Shows presence of I5- poly-iodide

anions [I-I-I-I-I]-

Implies M(dpg)2I formulated:

Pd
(d) I2
[M(dpg)20.2+](I5-)0.2
500 400 300 200 100
52
Wavenumber (cm-1)
 IR and Raman Vibrational Spectroscopy
Virtual
Energy States

Vibrational
Energy States
Infrared Rayleigh Stokes Anti-Stokes
Absorption Scattering Raman Raman
Scattering Scattering
Elastic Inelastic 53
(no energy loss) (energy loss or gain)
Basics of Poly-Iodides In q-

54
 MÖSSBAUER 129I
CHARACTERIZATION OF
Three sets of OXIDIZED STACK
8-line QS
patterns of 3
distinct I sites
Diagnostic 129I gamma-ray excitations of transitions
between energy levels in nuclei provides Mössbauer
isomer shifts and 8-line, I = 7/2 (2I+ 1 = 8) quadrupole
splitting patterns that are compared to reference
sample to show presence of the three distinct iodine
sites in V-shaped I5- units
XPS shows M(II) oxidation state
Hence, this suggests partial oxidation of ligand
Reference
sample Implies M(dpg)2I must be formulated:
containing I5-

[M(dpg)20.2+](I5-)0.2
55
Mössbauer Effect Basics
Nuclear Gamma Ray Spectroscopy

56
X-Ray Photoelectron Spectroscopy XPS Basics

57
 Perspective view
down the c-axis of
the unit cell of
[Ni(dpg)2](I5)0.2 where
dotted lines show the
dpg O-H-O hydrogen
bonds

• Staggered dpg structure – steric effect of phenyls?

• I2 doping reduces Ni-Ni distance from 3.547Å  3.223Å
• Linear I5- poly-halide anion resides between stacks
58
ELECTRICAL Electrical Conductivity Trend
PROPERTIES OF sNi(dpg)2  10-9 -1cm-1
“Ni(dpg)2I” sNi(dpg)2I  10-3 -1cm-1
sPd(dpg)2  10-9 -1cm-1
sPd(dpg)2I  10-5 -1cm-1

• 104-106 increase in s on doping

• Shorter Ni-Ni bond than Pd-Pd bond
• Better dpg -orbital overlap
• Wider dpg -CB
• Larger dE/dk = μe (d2E/d2k  1/m*)
• Larger me,h Smaller me,h*
s(Ni) > s(Pd)
59
Materials Food for Thought
Using structure-property-conductivity
physicochemical principles and relations, explain
what you would expect for the platinum analogues
in the series below:
sNi(dpg)2  10-9 -1cm-1
sNi(dpg)2I  10-3 -1cm-1
sPd(dpg)2  10-9 -1cm-1
sPd(dpg)2I  10-5 -1cm-1
sPt(dpg)2  ? -1cm-1
sPt(dpg)2I  ? -1cm-1
61
How would you synthesize NixPd1-x(dpg)2?
What are the different structures this mixed-metal
diphenylglyoxime stack could adopt for 0  x  1?
Rationalize how the electrical conductivities would
vary for these different stack structures for the
oxidized NixPd1-x(dpg)2I.

62
Which chemical and physical methods proved to be
the most informative in providing useful information
about the synthesis, structure, bonding, properties
relations of M(dpg)2 and its reaction with I2?

63
GETTING MACROCYCLES INTO COLUMNS
MAKING INTRASTACK BONDS
M • Stackers by chance
M • VdW interactions between stackers
M • crystal packing interactions between stacks
M • difficult to control
M •  electron interaction
•  band for the conductivity
M • Stackers by design
M • chemical bonded stackers
• fixes geometry
M • controls architecture
M • 1D polymeric conductor
•  electron interaction
M •  band for the conductivity 64
Structure of {Si(Pc)O}n N
N N
N
OH
N
Si
N N
N
N
N N O
N
N
Si
N N
N N
OH N N
N
N
Si
N N
Si, Ge, Sn N
O

• Structurally enforced 1D polymer wire

N
N N
N
• Electrically conductive metallo- N
Si
N N
macrocycle polymer chain N

65
SYNTHESIS OF SILICON PHTHALOCYANINES
Si ideal central atom because of short and strong covalent bonds.
Cl

N
N N
H N
SiCl4 N N
N

N H N Si N + 2 HCl
N N N
N N
N
Cl

Si switches from 2 H2 O
OH
common
tetrahedral into N N
N
N
Si
rarer octahedral N
N N Stable at room temperature
N
coordination. OH

• Besides Si also Ge, Sn can be used.

• Ge, Sn inserted under milder conditions – why is this?
• Fit better into the macro-cycle
• Ge, Sn stronger preference for higher coordination numbers 66
Materials Food for Thought
Concerning the chemistry shown on the previous slide, it is
found that besides Si also Ge and Sn can insert into the
phthalocyanine and form the polymer in a similar way. One
finds however that GeCl4 and SnCl4 inserted at a higher rate
and under milder conditions.

Q. Describe the chemical and physical principles that can

explain this behavior.

Q. What other main group metal halides might work in this

way? Provide some advantages of polymeric materials.
{Si(Pc)O}n a co-facially
linked stacked
N

semiconducting polymer N
N
N
Si
N
N
N
N
O
OH
d(Si-O-Si) = 3.3Å
N
Heat loss of H2O N
N
N N
N N
Si N
N
Si
N N N
N N
N
N
OH
Condensation O

polymerization
N
SiOH + HOSi  N N
N
Si-O-Si + H2O N
Si
N N
N

Insulating because of full bands

Polymer is soluble in concentrated sulfuric acid without decomposition!!!
68
 Oxidative Doping Chemistry of {M(Pc)O}n

[M(Pc)O]n  0.55n X 2  {[M(Pc)O]X1.1}n X  Br, I

“Nitrosonium”

[M(Pc)O]n  0.35n NO  Y -  {[M(Pc)O]Y0.35}n  0.35nNO

Y  BF4 , PF6 , SbF6
[M(Pc)O]n  nyQ  {[M(Pc)O]Qy }n

Q = Quinones (and their derivatives)

NC CN
O
Cl CN
Q=
Cl CN
O
NC CN
(Tetracyanoquinodimethane)
69
Structure of Oxidatively Doped {M(Pc)OI1.1}n

• staggered Pc

• poly-anion chain

• aligned in spaces
between Pc columns

70
OXIDATIVE DOPING OF {Si(Pc)O}n

As-Synthesized Annealed
As-Synthesized Doped tetragonal
Doped orthorhombic
Un-doped Thermodynamically
Metastable form
Stable form

Oxidative doping of {Si(Pc)O}n yields

different polymorphs
71
 Oxidative Chemical Doping of {Si(Pc)O}n
[Ox]

[Ox] = I2, Br2, NO+BF4, Q orthorhombic tetragonal

NC CN
O
Cl CN
Q= s
Cl CN
O
NC CN

0 % doping 100
Heterogeneous dopant uptake leads to mixture of orthorhombic phase and tetragonal
phase - s shows an abrupt discontinuity – percolation threshold
• Maximum chemical partial oxidation of 1/3 [PcSiO]n 5.5 x 10-6  cm-1
• Conductivity does not vary much with type of dopant
• Results in air stable, well-defined semiconducting polymers [PcSiOI1.1]n 6.7 x 10  cm
-1 -1
72
 Percolation Doping Threshold (Pc)
e-
Doped
region
e- Pc
e- s
Un-doped
region
e- 0 100
Volume Fraction

Heterogeneous random uptake of doping agent

• During oxidation, material is composed of doped and un-doped regions of varying dimensions
• Conductivity (s) shows an abrupt discontinuity at the Percolation Threshold (Pc )
• Typical for any material containing a mixture of conductive & insulating phases
• s dramatically increases when volume fraction is reached where a continuous network of contacting
conductive particles is maintained and charge can hop or tunnel from particle to particle
73
Electrosynthesis and Electrocrystallization of Doped {M(Pc)O}r+rX-
on Working Electrode
Potentiostat

Pt mesh Separator Ag reference

(counter) membrane

[Si(Pc)O]n
Pt mesh
(working electrode)

Electrolyte Electrolyte
0.3 M TBABF4 0.3 M TBABF4

Right-hand Side: {Si(Pc)O}  {Si(Pc)O}r+ + re-

Left-hand Side: Bu4N+ + e-  Bu4N•  Bu3N + ½ Bu2 74

Electrosynthesis and
Electrochemistry
Electrocrystallization
of {Si(Pc)O} y+
of Doped {M(Pc)O}r+rX-
n
on Working Electrode
Reduction

• First cycle: doping into orthorhombic crystal

Un-doping Subsequent cycles: doping into tetragonal
form
2 Tetragonal – Electrochemical annealing of structure to
Doping polymorph
3 most stable polymorph!
1 • Electrochemical tuning of electron bands
Orthorhombic filling/emptying
polymorph – Enables tuning conductivity and optical
properties of polymer!

Oxidation

Eapplied / V
75
Factors that Control Electronic Properties of {M(Pc)O}r+rX-
r+ r+
X- Why not
metallically
d CB conductive?
r+ r+
X-

r+ r+ VB
X-

d’
Degree of doping (r+) controls degree of band filling, band width, band
curvature, electron mobility, effective mass and electrical conductivity
• Interstack (d’) vs. intrastack (d) separation differences (dSi < dGe < dSn)
• Cation stacks stabilized by interaction with anions
• Determines optical properties and inter-/intra-stack conductivities
• Behaves as p-type activated hopping semiconductors (σSi > σGe > σSn) 76
 Structure
Property Trends
and Processing
Processing
• Dissolve {Si(Pc)O}n in CF3SO3H
• Blend with Kevlar
-1

• Extrude to fibre
• Oxidative doping (polyhalide counter-anions)
• Conductive fibre!

σSi > σGe > σSn

-1

H H O O
N N C C

Kevlar
-8
(Poly-parapheylene terepthalamide)

77
 Materials Food for Thought

Explain the structure-doping-conductivity

trends of the {M(Pc)O}n polymeric materials
shown in the following three slides.

78
Structure-Doping-Conductivity Trends

{Si(Pc)O} 5.5x10-6 -1 cm-1

{Ge(Pc)O} 2.2x10-10 -1 cm-1

{Sn(Pc)O} 1.2x10-9 -1 cm-1

Un-doped {Si(Pc)O}n
• Full VB
• Pc-M-Pc distance: controls p-p Pc orbital overlap
• VB-CB width: controls electronic band gap (Eg)
• Semiconductor energy gap law regarding conductivity
79
 Structure-Doping-Conductivity Trends

{Si(Pc)O}I0.12 1. 4x10-3 -1 cm-1

{Ge(Pc)O}I0.14 2.5x10-6 -1 cm-1

{Sn(Pc)O}I0.14 5.2x10-9 -1 cm-1

Low-level Doping of {Si(Pc)O}n

• Partially filled VB
• Pc-M-Pc distance: controls p-p Pc orbital overlap
• VB-CB width: controls electronic band gap (Eg)
• Semiconductor energy gap law regarding conductivity
• p-type hopping semiconductor
80
 Structure-Doping-Conductivity Trends

Structural Features
• {Si(Pc)O} 5.5x10-6 -1 cm-1 • Pc-Si-Pc charge
• Pc-Si-Pc distance
• {Si(Pc)O}I0.12 1.4x10-3 -1 cm-1
• Pc-Si-Pc overlap
• {Si(Pc)O}I0.23 1.7x10-2 -1 cm-1 • Inter-stack interactions
• Partially filled VB
• {Si(Pc)O}I0.31 7.6x10-2 -1 cm-1
• {Si(Pc)O}I0.71 3.2x10-1 -1 cm-1 Conductivity Effects:
• Degree of band filling
• {Si(Pc)O}I1.20 5.8x10-1 -1 cm-1 • Band width
• Band curvature
• {Si(Pc)O}I1.30 6.7x10-1 -1 cm-1 • Electron mobility (me)
• Effective electron mass (m*)
• {Si(Pc)O}I1.55 1.4x100 -1 cm-1
• p-type hopping semiconductor
• Intra-/inter-chain conductivity
81
Degree of Electronic Band Filling Determines Electrical Conductivity

𝑑𝐸
𝜇∝
𝑑𝑘
−1
𝑑𝐸
𝑚∗ ∝
𝑑𝑘

82
Macrocycles in Sheets – Forming Interstack Linkages

M M Stackers by design
• Chemically bonded stackers
M M M M
• Fixed geometry
M M M M
• Controlled architecture
M M M M
• 2D polymeric conductor
M M M M
• -electron interactions
M M • -band controls conductivity

83
Chemically Linking Phthalocyanines into 2D
Covalent Organic Frameworks

Chem. Soc. Rev. 2012, 41, 6010–6022

84
Chemically Linking Phthalocyanines into
2D Covalent Organic Frameworks
• Choice of stacker units provides control over
electron density and pore diameter in COFs

85
Oxidatively Doped p-Type Hopping Semiconductor MPc-COFs

86
Liquid Crystals: An Intermediate Phase of Matter

Crystal Liquid Crystal Liquid

87
Some Classes of Liquid Crystals

• Nematic: Parallel stacking of rods

• Smectic: Parallel stacking + vertical stacking
of multiple layers
• Discotic columnar: Vertical stacking of
discs

• Liquid crystals may also be chiral, allowing

them to interact with polarized light!

88
 Diffracted Colour from Liquid Crystals

• A chiral nematic liquid crystal phase

• Bragg diffraction of light when helical pitch =  of light
• Temperature can be used to increase the pitch and hence
shift diffracted color to longer wavelengths
•  Thermochromic material!
89
Applications of Chiral Nematic Thermochromic Liquid Crystals

90
Temperature-tunable Colour
Stacked Macrocycle Liquid Crystals

Thermochromic Liquid Crystals

Structural Color from Optical Diffraction
 How Can We Understand this Behaviour?

Temperature-dependent Electronic and Optical Properties

of Macrocyclic Metal Glyoximates,
1D Liquid Crystal Materials
 Temperature-tunable Colour from Stacked Macrocycles
Direct Visualization of van der Waals Interactions in 1D Inorganic–Organic Stacked Macrocycles
using M–M Bond Optical Absorption Spectroscopy

R R
R R
H
O O
N N
M
N N
O O
H
R R
R R

M=Ni, Pd, Pt R=OCnH2n+1

93
 Temperature-tunable Colour from Stacked Macrocycles
Synthesis of Building Blocks

94
J. Mater. Chem. 1998, 8, 1971.
 Thinking About Bonds to Bands in MX4
Square planar D4h M(II) complex
px,y • Orbitals filled up to ndz2.
pz • These d8 M(II) complexes
(n+1)p form in-plane bonds using
dx2-y2
metal’s s, p2x,y, and dx2-y2
1 2
(n+1)s
dz2 1. Dipole allowed M M optical
transition: ndz2  (n+1)pz.
nd dyz,xz,xy
2. Dipole allowed MLCT optical
transition: ndz2  (n+1)px,y
Ni or Pt 4L

L
L Pt L
L 95
Consider Two MX4 Molecules in Eclipsed Conformation:

L L
σ-bonding π-bonding
L L
Pt Pt
L L pz pz
dxz,yz dxz,yz
L L

s(pz)
dz2 dz2 dxy,x2-y2 dxy,x2-y2
d
Observed electronic structure:
• wide, empty pz σ-band
• wide, filled dz2 σ-band
s(dz2) • narrow, filled dxy,xz,yz and dx2-y2 bands
Orbital symmetry and overlap controls:

• band width and band gap
d • controls M–M distance
Band filling-width controls conductivity
96
 Observing Thermochromic Behaviour
via the ndz2  (n+1)pz Transition
A band: M  M
B band: MLCT
• Increased temperature results in
blue shift of ndz2  (n+1)pz
transition, implying narrowing of
associated bands
• Resulting band gap (Eg) increase
and M–M interaction energy
decrease due to increasing M–M
distances

97
 Consider Two MX4 Molecules in Eclipsed Conformation:
R
• Same alkane chain length, different
R
R R
H
O O Pd
N
M
N metal center
N
Ni
N

R
O
H
O

Pt
• Higher temperature weakens intra-
R
R R
chain VdW interactions
M=Ni, Pd, Pt R=OCnH2n+1

• Manifests as decreasing M–M

interaction between macrocycles,
decreasing bandwidth and increasing
ndz2  (n+1)pz energy gap (blue shift)
• Manifests as smaller apparent VdW
intra-chain pressure between
macrocycles
98
 Consider Two MX4 Molecules in Eclipsed Conformation:
R
R

H
R
R • Greater alkane chain length, same
O
O
N N metal center
M
N
• Causes larger VDW interactions
N
O O
H
R R
R R

M=Ni, Pd, Pt R=OCnH2n+1

• Manifests as increasing M–M
interaction between centers;
hence, wider s bands and
decreasing ndz2  (n+1) energy
gap (red shift)
• Manifests as greater apparent
VdW intra-chain pressure between
macrocycles
99
 Materials Food for Thought

For these one-dimensional, thermochromic macrocyclic

metal glyoximates, explain the non-monotonic order of the
temperature dependence of the ndz2  (n+1)pz optical
transition for Ni, Pd, and Pt, which gives rise to their color?
Can you think of an application for these temperature-
sensitive, color-tunable materials?
What properties of these materials would you expect to
change if you selectively photo-excited the ndz2  (n+1)pz
optical transition?
 Materials Food for Thought

For these one-dimensional, alkane-functionalized

nickel glyoximate macrocycles, explain the
physicochemical principles that underpin the red
shift of the ndz2  (n+1)pz optical transition as a
function of pressure?
Can you think of an application for this kind of
pressure-sensitive, color-tunable liquid crystal
material?
 Materials Food for Thought

How would you make a thermometer using a 1,2-

diketone, hydroxylamine and nickel chloride?
(Provide relevant synthesis, structure, property and
function details that explain the formation and operation
of this temperature-measuring device.)
What’s Next ?

Just imagine!
103