Macromolecules Containing Metal and

This volume in the series covers nanoscale interactions of metal-containing polymers; chapters include "Nanoscale Clusters and Molecular Orbital Interactions in Macromolecular-Metal Complexes", "Metal Oxide Clusters as Building Blocks for Inorganic-Organic Hybrid Polymers", and more.

Dr. Alaa Abd-El-Aziz is Professor of Chemistry and the Associate Vice-President of Research & Graduate Studies at the University of Winnipeg.

Dr. Charles Carraher is Professor of Chemistry at Florida Atlantic University and Associate Director of the Florida Center for Environmental Studies.

Dr. Charles Pittman has a B.S. in Chemical Engineering from Lafayette College and a Ph.D. in Organic Chemistry from Pennsylvania State University. He completed postdoctoral studies with G. A. Olah, and served on active duty at the U.S. Army University of Alabama. He was appointed Full Professor in 1975 and University Research Professor in 1977. Dr. Pittman came to Mississippi State in 1983 as Professor of Industrial Chemistry and Catalysis. He is also Research Director of the University/Industry Chemical Research Center.

Martin Zeldin is Visiting Senior Research Scholar at the University of Richmond in Virginia. He received his Ph.D. in inorganic chemistry in 1968 from Pennsylvania State University.

Preface

xiii

Series Preface

xv

Nanocluster Assemblies and Molecular Orbital Interactions in Macromolecule-Metal Complexes

1

(54)

Laurence A. Belfiore

Sarah E. Fenton

Introduction

3

(1)

Methodology of Transition Metal Coordination in Polymeric Complexes

4

(14)

Polymeric Coordination Complexes with d-Block Salts that Exhibit an Increase in Tg

4

(1)

Chemical Bonding, Coordination, and Transition Metal Compatibilization

5

(1)

Ligand Field Stabilization Energy Description of the Enhancement in Tg for Polymeric Complexes with Transition Metals

6

(2)

Energetic Ligand Field Models and the Methodology of Transition Metal Coordination

8

(1)

Well-Defined Low-Molecular-Weight Transition Metal Complexes that Increase Tg

9

(1)

Attractive Polymeric Ligands

10

(1)

Identifying Attractive Interactions via Hard and Soft Acids and Bases

10

(1)

Displacement of Weak Neutral Bases in the First-Shell Coordination Sphere by Stronger Bases

11

(2)

Anionic Ligands are the Last Ones that Should Be Displaced to the Second Shell

13

(1)

Complexes with the Same Local Symmetry Above and Below the Glass Transition

14

(1)

Complexes with Reduced Symmetry Above Tg

14

(1)

Consideration of Interelectronic Repulsion and Ligand Field Splitting When There Is Ambiguity in the d-Electron Configuration

15

(3)

Jorgensen's Parametric Representation of Ligand Field Splitting and Interelectronic Repulsion

18

(2)

Polymeric Complexes with Enhanced Glass-Transition Temperatures

19

(1)

Polymeric Complexes with Reduced Glass-Transition Temperatures

20

(1)

Other Considerations

20

(1)

Pseudo-Octahedral d8 Nickel Complexes with Poly(4-vinylpyridine)

20

(7)

Ligand Field Stabilization Energies

20

(2)

Coordination Crosslinks vs. Coordination Pendant Groups

22

(2)

Ligand Field Model of the Glass Transition in Macromolecule-Metal Complexes

24

(2)

Linear Least Squares Analysis of Δ(LFSE) via the Concentration Dependence of Tg in P4VP/Ni2+ Complexes, Subject to the Constraint that β ≤1

26

(1)

d6 Molybdenum Carbonyl Complexes with Poly(vinylamine) that Exhibit Reduced Symmetry Above the Glass-Transition Temperature

27

(7)

Experimental Results

27

(1)

Ligand Field Splitting Parameters for Molybdenum Hexacarbonyl

28

(1)

Ligand Field Stabilization for Complexes of Molybdenum Hexacarbonyl and Poly(vinylamine) in the Glassy State

29

(1)

Quantum Mechanical Model Parameters and Trigonal Bipyramid 5-Coordinate d6 Complexes of Molybdenum Hexacarbonyl and Poly(vinylamine) with D3h Symmetry Above Tg

29

(2)

Square Pyramid 5-Coordinate d6 Complexes of Molybdenum Hexacarbonyl and Poly(vinylamine) with C4v Symmetry Above Tg

31

(1)

Pentagonal Planar 5-Coordinate d6 Complexes of Molybdenum Hexacarbonyl and Poly(vinylamine) with D5h Symmetry Above Tg

32

(1)

Ligand Field Stabilization of 5-Coordinate d6 Complexes of Molybdenum Hexacarbonyl and Poly(vinylamine) Above Tg

33

(1)

Cobalt, Nickel, and Ruthenium Complexes with Poly(4-vinylpyridine) and Poly(L-histidine) that Exhibit Reduced Symmetry in the Molten State

34

(14)

Polymeric Coordination Complexes with d-Block Salts

34

(3)

Ruthenium d6 Complexes

37

(1)

Cobalt d7 Complexes

37

(1)

Nickel d8 Complexes

38

(1)

d-Orbital Energies for Five-Coordinate Complexes above Tg

38

(1)

Trigonal Bipyramid dm Complexes with D3h Symmetry

38

(1)

Square Pyramid dn Complexes with C4v Symmetry

39

(1)

Pentagonal Planar dn Complexes with D5h Symmetry

39

(2)

Summary of LFSE Calculations for 5-Coordinate dn Complexes

41

(1)

Stabilization of Metal d-Electrons in Mixed-Ligand Complexes

41

(2)

Consideration of Interelectronic Repulsion and Δ0 When There is Ambiguity in the d-Electron Configuration for Complexes with Pseudo-Octahedral Symmetry

43

(1)

Correlation between Tg Enhancement and the Difference Between Ligand Field Stabilization Energies in the Glassy and Molten States

44

(2)

Tetrahedral Co2+ Complexes Below Tg and 3-Coordinate Complexes in the Molten State

46

(2)

Total Energetic Requirements to Induce the Glass Transition via Consideration of the First-Shell Coordination Sphere in Transition Metal and Lanthanide Complexes

48

(2)

Density Functional Estimates of Metal--Ligand Bond Dissociation Energies

48

(1)

The Energetics of Ligand Dissociation Reactions in Model Systems; Comparison with Experimental Tg Enhancements for d-Block and f-Block Complexes

49

(1)

Summary

50

(1)

Acknowledgments

51

(1)

References

51

(4)

Metal Oxide Clusters as Building Blocks for Inorganic-Organic Hybrid Polymers

55

(18)

Ulrich Schubert

Introduction

56

(2)

Synthesis of Organically Modified Transition Metal Oxide Clusters

58

(5)

Postsynthesis Modification of Pre-Formed Metal Oxide Clusters

59

(1)

In Situ Modification

59

(4)

Synthesis and Structural Characterization of the Cluster-Reinforced Polymers

63

(4)

Properties of the Cluster-Based Hybrid Polymers

67

(2)

Summary

69

(1)

Acknowledgments

69

(1)

References

70

(3)

Metal-Containing Polydyes

73

(14)

Charles E. Carraher Jr.

Introduction

73

(1)

Group IVB-Containing Polydyes

74

(6)

Ruthenium-Containing Polydyes

80

(2)

Hematoporphyrin-Containing Polydyes

82

(3)

Summary

85

(1)

References

85

(2)

Metallopolymer Nanocomposite-Macromolecular Metallocomplexes as Precursors for Polymers, Polymer Inorganics, and Bionanocomposites

87

(134)

A. D. Pomogailo

Introduction

89

(2)

General Characteristics, Classification of Nanoparticles by Size, Structural Organization, and Dimensional Phenomena

91

(11)

Problems of Stabilization of Metal Nanoparticles by Polymers

102

(6)

Basic Considerations of the Combinations of Macromolecules and Metals

108

(5)

Typical Formation Processes and the Structure of Nanometric Metal Particles in Polymers

113

(22)

Technique of the Atomic Metal Evaporation

113

(4)

Preparation of Polymer-Immobilized Nanoparticles by Plasma Polymerization

117

(3)

Preparation of Metal Sols in Polymers by the Thermal Decomposition of Precursor Compounds

120

(8)

Synthesis of Polymer-Immobilized Nanoparticles by Reductive Methods

128

(4)

Electrochemical Methods for Preparing Polymer-Immobilized Nanoparticles

132

(1)

Preparation of Polymer-Immobilized Nanoparticles During Polymerization (Polycondensation) Stage

133

(2)

Preparation of Hybrid Nanocomposites by the Sol-Gel Method

135

(13)

Sol-Gel Prepartion of Nanohybrid Multimetallic Materials

148

(10)

Intercalation of Polymers Into Porous and Layered Nanostructures

158

(8)

Metal Chalcogenide-Polymer Inclusion Nanocomposites

166

(3)

Metallopolymeric Langmuir-Biodgett Films-Self-Organized Hybrid Nanocomposites

169

(5)

Nanometer-Size Particles, Clusters, and Polynuclear Structures Immobilized in Biopolymers and Their Analogs

174

(11)

The Formation of Metallobiopolymeric Systems

175

(6)

Polynuclear Metalloenzymes as Components of Nanobiocomposites

181

(1)

Preparation of Template Synthetic Nanobiocomposites by the Sol-Gel Method

182

(3)

Application of Polymer-Immobilized Metal Nanoparticle and Metal Cluster Nanocomposites

185

(10)

Modification of Polymer Matrices by Nanoparticles

186

(2)

Electrical and Magnetic Properties

188

(2)

Polymer-Immobilized Nanoparticles as Optical Materials and Semiconductors

190

(2)

Catalysis Using Polymer-Immobilized Nanoparticles and Clusters

192

(3)

Conclusion

195

(2)

Acknowledgments

197

(1)

References

198

(23)

Index

221

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Macromolecules Containing Metal and Metal-Like Elements, Nanoscale Interactions of Metal-Containing Polymers

Summary

Author Biography

Table of Contents

Supplemental Materials

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Macromolecules Containing Metal and Metal-Like Elements, Nanoscale Interactions of Metal-Containing Polymers

Summary

Author Biography

Table of Contents

Supplemental Materials

Digital License