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

Macromolecules Containing Metal and Metal-Like Elements Volume 7......Page 3
Contributors......Page 7
Contents......Page 9
Preface......Page 15
Series Preface......Page 17
1. Nanocluster Assemblies and Molecular Orbital Interactions in Macromolecule-Metal Complexes......Page 19
I. Introduction......Page 21
A. Polymeric Coordination Complexes with d-Block Salts that Exhibit an Increase in T(g)......Page 22
B. Chemical Bonding, Coordination, and Transition Metal Compatibilization......Page 23
i. Ligand Field Stabilization Energy Description of the Enhancement in T(g) for Polymeric Complexes with Transition Metals......Page 24
ii. Energetic Ligand Field Models and the Methodology of Transition Metal Coordination......Page 26
C. Well-Defined Low-Molecular-Weight Transition Metal Complexes that Increase T(g)......Page 27
E. Identifying Attractive Interactions via Hard and Soft Acids and Bases......Page 28
F. Displacement of Weak Neutral Bases in the First-Shell Coordination Sphere by Stronger Bases......Page 29
i. Anionic Ligands are the Last Ones that Should Be Displaced to the Second Shell......Page 31
i. Complexes with Reduced Symmetry Above T(g)......Page 32
H. Consideration of Interelectronic Repulsion and Ligand Field Splitting When There Is Ambiguity in the d-Electron Configuration......Page 33
III. Jørgensen’s Parametric Representation of Ligand Field Splitting and Interelectronic Repulsion......Page 36
A. Polymeric Complexes with Enhanced Glass-Transition Temperatures......Page 37
A. Ligand Field Stabilization Energies......Page 38
B. Coordination Crosslinks vs. Coordination Pendant Groups......Page 40
C. Ligand Field Model of the Glass Transition in Macromolecule–Metal Complexes......Page 42
D. Linear Least Squares Analysis of D(LFSE) via the Concentration Dependence of T(g) in P4VP/Ni(2+) Complexes, Subject to the Constraint that b 1......Page 44
A. Experimental Results......Page 45
B. Ligand Field Splitting Parameters for Molybdenum Hexacarbonyl......Page 46
D. Quantum Mechanical Model Parameters and Trigonal Bipyramid 5-Coordinate d(6) Complexes of Molybdenum Hexacarbonyl and Poly(vinylamine) with D(3h) Symmetry Above T(g)......Page 47
E. Square Pyramid 5-Coordinate d(6) Complexes of Molybdenum Hexacarbonyl and Poly(vinylamine) with C(4v) Symmetry Above T(g)......Page 49
F. Pentagonal Planar 5-Coordinate d(6) Complexes of Molybdenum Hexacarbonyl and Poly(vinylamine) with D(5h) Symmetry Above T(g)......Page 50
G. Ligand Field Stabilization of 5-Coordinate d(6) Complexes of Molybdenum Hexacarbonyl and Poly(vinylamine) Above T(g)......Page 51
A. Polymeric Coordination Complexes with d-Block Salts......Page 52
C. Cobalt d(7) Complexes......Page 55
i. Trigonal Bipyramid d(n) Complexes with D(3h) Symmetry......Page 56
iii. Pentagonal Planar d(n) Complexes with D(5h) Symmetry......Page 57
G. Stabilization of Metal d-Electrons in Mixed-Ligand Complexes......Page 59
H. Consideration of Interelectronic Repulsion and D(0) When There is Ambiguity in the d-Electron Configuration for Complexes with Pseudo-Octahedral Symmetry......Page 61
I. Correlation between T(g) Enhancement and the Difference Between Ligand Field Stabilization Energies in the Glassy and Molten States......Page 62
J. Tetrahedral Co(2+) Complexes Below T(g) and 3-Coordinate Complexes in the Molten State......Page 64
A. Density Functional Estimates of Metal–Ligand Bond Dissociation Energies......Page 66
B. The Energetics of Ligand Dissociation Reactions in Model Systems; Comparison with Experimental T(g) Enhancements for d-Block and f-Block Complexes......Page 67
VIII. Summary......Page 68
X.References......Page 69
2. Metal Oxide Clusters as Building Blocks for Inorganic-Organic Hybrid Polymers......Page 73
I. Introduction......Page 74
II. Synthesis of Organically Modified Transition Metal Oxide Clusters......Page 76
B. In Situ Modification......Page 77
III. Synthesis and Structural Characterization of the Cluster-Reinforced Polymers......Page 81
IV. Properties of the Cluster-Based Hybrid Polymers......Page 85
VI. Acknowledgments......Page 87
VII. References......Page 88
I. Introduction......Page 91
II. Group IVB–Containing Polydyes......Page 92
III. Ruthenium-Containing Polydyes......Page 98
IV. Hematoporphyrin-Containing Polydyes......Page 100
VI. References......Page 103
4. Metallopolymer Nanocomposite-Macromolecular Metallocomplexes as Precursors for Polymers, Polymer Inorganics, and Bionanocomposites......Page 105
I. Introduction......Page 107
II. General Characteristics, Classification of Nanoparticles by Size, Structural Organization, and Dimensional Phenomena......Page 109
III. Problems of Stabilization of Metal Nanoparticles by Polymers......Page 120
IV. Basic Considerations of the Combinations of Macromolecules and Metals......Page 126
A. Technique of the Atomic Metal Evaporation......Page 131
B. Preparation of Polymer-Immobilized Nanoparticles by Plasma Polymerization......Page 135
C. Preparation of Metal Sols in Polymers by the Thermal Decomposition of Precursor Compounds......Page 138
D. Synthesis of Polymer-Immobilized Nanoparticles by Reductive Methods......Page 146
E. Electrochemical Methods for Preparing Polymer-Immobilized Nanoparticles......Page 150
F. Preparation of Polymer-Immobilized Nanoparticles During Polymerization (Polycondensation) Stage......Page 151
VI. Preparation of Hybrid Nanocomposites by the Sol-Gel Method......Page 153
VII. Sol-Gel Prepartion of Nanohybrid Multimetallic Materials......Page 166
VIII. Intercalation of Polymers Into Porous and Layered Nanostructures......Page 176
IX. Metal Chalcogenide-Polymer Inclusion Nanocomposites......Page 184
X. Metallopolymeric Langmuir-Biodgett Films–Self-Organized Hybrid Nanocomposites......Page 187
XI. Nanometer-Size Particles, Clusters, and Polynuclear Structures Immobilized in Biopolymers and Their Analogs......Page 192
A. The Formation of Metallobiopolymeric Systems......Page 193
B. Polynuclear Metalloenzymes as Components of Nanobiocomposites......Page 199
C. Preparation of Template Synthetic Nanobiocomposites by the Sol-Gel Method......Page 200
XII. Application of Polymer-Immobilized Metal Nanoparticle and Metal Cluster Nanocomposites......Page 203
A. Modification of Polymer Matrices by Nanoparticles......Page 204
B. Electrical and Magnetic Properties......Page 206
C. Polymer-Immobilized Nanoparticles as Optical Materials and Semiconductors......Page 208
D. Catalysis Using Polymer-Immobilized Nanoparticles and Clusters......Page 210
XIII. Conclusion......Page 213
XIV. Acknowledgments......Page 215
XV. References......Page 216
Index......Page 239