Inorganic Materials

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ISBN: 9780471960362 | 0471960365
Cover: Paperback
Copyright: 7/9/1997

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Given the recent expansion in materials chemistry, this book addresses several of the vigorous areas of research in this field, where inorganic materials are central to the research. Each chapter provides an introduction to the subject under discussion and then develops the field to provide a sensible overview, with certain topics being expanded. Written by an international group of researchers the nine chapters cover such important areas as inorganic superconductors, magnetic materials, biogenic inorganic materials, polymeric co-ordination compounds, liquid crystals and precursors for electronic materials.

List of Contributors

xiv

1 Molecular Inorganic Superconductors

(64)

Patrick Cassoux and Lydie Valade

1.1 Background

(5)

1.1.1 The KCP Complexes

(2)

1.1.2 The Organic Metals

(2)

1.2 Use of Guidelines for Selecting Candidate Systems

(5)

1.2.1 Laying Down the Guidelines

(1)

1.2.2 Application to Molecular Inorganic Conductors

(2)

1.2.3 One-dimensionality versus Two-dimensionality

(1)

1.2.4 The [M(dmit)2] Complexes

(1)

1.3 The Synthesis of Conductors and Superconductors Based on [M(dmit)2] Complexes

(8)

1.3.1 The dmit Ligand

(2)

1.3.2 The [C]n[M(dmit)2] Precursor Complexes

(1)

1.3.3 The [C]x[M(dmit)2] Non-integral Oxidation State Complexes

(3)

1.3.4 The [D][M(dmit)2]y Donor—acceptor Compounds

(3)

1.4 Questions Related to the [M(dmit)2] Systems

(8)

1.4.1 May the [M(dmit)2] Chains Alone be Conducting and Superconducting ?

(1)

1.4.2 Patrick Cassoux and Ludic Valade

1.4.2 What is the Oxidation State in these Systems 7

(3)

1.4.3 Are the [M(dmit)2] Systems Polymorphic 7

(2)

1.4.4 Is Regular Stacking a Prerequisite to Metal-like Conductivity or Superconductivity 7

(1)

1.4.5 Is Metal-like Behaviour down to Low Temperatures a Prerequisite to Superconductivity 7

(1)

1.5 Dimensionality and the Origin of Superconductivity in [M(dmit)2]-based Superconductors

(17)

1.5.1 Structure and Dimensionality of [M(dmit)2]-based Superconductors

(4)

1.5.2 Electrical Properties of [M(dmit)2]-based Superconductors

(6)

1.5.3 Phase Diagrams of α'-[TTF][Pd(dmit)2]2 and [TTF][Ni(dmit)2] 2

(3)

1.5.4 Charge-density-wave Condensations in α'-[TTF][Pd(dmit)2]2 and [TTF][Ni(dmit)2]2

(3)

1.5.5 Intermediate Conclusions

(1)

1.6 Band Structure Calculations and General Discussion

(4)

1.6.1 Band Structure Calculations

(2)

1.6.2 General Discussion

(2)

1.7 Conclusion

(2)

1.8 Update

(5)

1.8.1 The β-[Me4N0.5[Pd(dmit)2] Phase

(2)

1.8.2 The [Me2Et2N]0.5[Pd(dmit)2] Compound

(1)

1.8.3 The α-[EDT-TTF][Ni(dmit)2] Phase

(1)

1.8.4 CDW Instabilities in [EDT-TTF][M(dmit)2] Compounds

(2)

1.8.5 Conclusion

(1)

1.9 Acknowledgements

(1)

1.10 References

(9)

2 Molecular Inorganic Magnetic Materials

(56)

Olivier Kahn, Yu Pei and Yves Journaux

2.1 Introduction

(1)

2.2 Some Generalities in Molecular Magnetism

(5)

2.2.1 Definitions and Units

(1)

2.2.2 Fundamental Equations

(2)

2.2.3 Molecules Containing a Unique Magnetic Centre

(2)

2.3 Interaction in Binuclear Compounds

(5)

2.3.1 Isotropic Interaction in Binuclear Compounds

(4)

2.3.2 Dipolar, Anisotropic and Antisymmetric Interactions

(1)

2.4 Magnetic Chain Compounds

(12)

2.4.1 Chains of Equally Spaced Ions

(4)

2.4.2 Regular Ferrimagnetic Chains; Theory

(4)

2.4.3 Regular Ferrimagnetic Chains; Some Examples

(3)

2.4.4 Alternating Ferrimagnetic Chains

(1)

2.5 Magnetic Long-Range Ordering in Molecular Compounds

(27)

2.5.1 Three-dimensional Magnetic Ordering and Molecular-based Ferromagnets

(3)

2.5.2 Orbital Degeneracy and Ferromagnetic Interaction

(3)

2.5.3 Ferromagnetic Transition in Decamethylferrocenium Tetracyanoethenide

(6)

2.5.4 Ferromagnetic Ordering of Ferrimagnetic Chains

101

(11)

2.5.5 Other Strategies to Design Inorganic Molecular-based Ferromagnets

112

(4)

2.6 Conclusion

116

(1)

2.7 References

117

(4)

3 Metal-containing Materials for Nonlinear Optics

121

(50)

Seth R Marder

3.1 Overview

122

(1)

3.2 Basic Concepts of Nonlinear Optics

122

(17)

3.2.1 The Big Picture

122

(1)

3.2.2 Polarisability: A Microscopic View

123

(3)

3.2.3 Linear Polarisation of Matter and Linear Optical Effects

126

(1)

3.2.4 Nonlinear Polarisability: A Microscopic View

127

(4)

3.2.5 Second-order Nonlinear Polarisation of Matter and Second-order NLO Effects

131

(2)

3.2.6 Third-order Nonlinear Polarisation of Matter and Third-order NLO Effects

133

(4)

3.2.7 Engineering Linear and Nonlinear Polarisability

137

(2)

3.3 Nonlinear Optical Properties of Organometallic and Coordination Compounds

139

(25)

3.3.1 Motivation for Studying Organometallic and Coordination Compounds for Nonlinear Optics

139

(1)

3.3.2 Second-order Materials

140

(13)

3.3.3 Third-order Materials

153

(11)

3.4 Acknowledgements

164

(1)

3.5 References

165

(6)

4 Inorganic Intercalation Compounds

171

(84)

Dermot O'Hare

4.1 Introduction

172

(7)

4.1.1 General Considerations

172

(7)

4.2 The Kinetics and Mechanism of Intercalation

179

(5)

4.2.1 Introduction

179

(1)

4.2.2 Staging

179

(2)

4.2.3 Kinetic Measurements

181

(3)

4.3 Synthetic Methods

184

(7)

4.3.1 Introduction

184

(1)

4.3.2 Direct Reaction

184

(3)

4.3.3 Ion Exchange

187

(1)

4.3.4 Swelling, Flocculation and Reflocculation

188

(1)

4.3.5 Electrointercalation Methods

189

(1)

4.3.6 Rate Enhancement Methods

190

(1)

4.4 Lamellar Host Lattices and their Intercalates

191

(46)

4.4.1 Introduction

191

(1)

4.4.2 The Metal Dichalcogenides

191

(11)

4.4.3 The Metal Oxyhalides

202

(6)

4.4.4 The Metal Phosphorus Trisulphides

208

(7)

4.4.5 The Metal Oxides

215

(6)

4.4.6 The Metal Phosphates and Phosphonates

221

(7)

4.4.7 Graphite

228

(2)

4.4.8 Layered Silicates, Clay Minerals and Double Hydroxides

230

(5)

4.4.9 Other Layered Host Lattices

235

(2)

4.5 Chain Structure Host Lattices and their Intercalates

237

(2)

4.5.1 Introduction

237

(1)

4.5.2 Niobium Triselenide

237

(1)

4.5.3 Other One-Dimensional Systems

238

(1)

4.6 Framework Hosts and their Intercalates

239

(3)

4.6.1 Introduction

239

(1)

4.6.2 Zeolites

239

(1)

4.6.3 Sodium β-Alumina

240

(1)

4.6.4 Tungsten Trioxide

241

(1)

4.7 Molecular Hosts and their Intercalates

242

(1)

4.7.1 Introduction

242

(1)

4.7.2 C60

242

(1)

4.8 Conclusions

243

(1)

4.9 References

244

(11)

5 Biogenic Inorganic Materials

255

(58)

Stephen Mann

5.1 Introduction

256

(2)

5.2 Biominerals; Types and Functions

258

(8)

5.2.1 Calcium Carbonate

259

(2)

5.2.2 Calcium Phosphate

261

(2)

5.2.3 Other Calcium Biominerals

263

(1)

5.2.4 Iron Oxides

263

(1)

5.2.5 Iron Sulphides

264

(1)

5.2.6 Silica

265

(1)

5.3 Crystal Engineering

266

(2)

5.4 Control Mechanisms

268

(38)

5.4.1 Mineralisation Sites

270

(1)

5.4.2 Solid State Chemistry in a Nanospace

271

(9)

5.4.3 Shaping the Mineralisation Space

280

(6)

5.4.4 Organised Assemblies

286

(7)

5.4.5 Morphology and Crystal Surfaces

293

(3)

5.4.6 Matrix-mediated Nucleation

296

(10)

5.5 Conclusions

306

(1)

5.6 References

307

(6)

6 Clay Chemistry

313

(64)

Richard W McCabe

6.1 Introduction

314

(11)

6.1.1 The Structure of Clay Minerals

314

(4)

6.1.2 Ion Exchange of Clays

318

(2)

6.1.3 Acidity of Clays

320

(2)

6.1.4 Acid Activation of Clays

322

(1)

6.1.5 Pillaring of Clays

322

(3)

6.1.6 Clays as Supports

325

(1)

6.2 Clay-Mediated Organic Reactions

325

(38)

6.2.1 Clays as Breasted Acids

326

(1)

6.2.2 Breasted Acid Catalysis

326

(16)

6.2.3 Lewis-acid-catalysed Reactions

342

(3)

6.2.4 Redox Reactions

345

(3)

6.2.5 Promotion of Reactions via Reactive Intermediates

348

(2)

6.2.6 Cycloaddition Reactions

350

(5)

6.2.7 Clays as a Support for Reagents and Catalysts

355

(8)

6.3 Conclusions

363

(1)

6.4 References

363

(14)

7 Polymeric Coordination Complexes: Bridging Molecular Metals and Conductive Polymers

377

(52)

Glen Eugene Kellogg and John G Gaudiello

7.1 Introduction

378

(13)

7.1.1 Charge-transfer Solids

381

(2)

7.1.2 Covalent-organic Arrays; Polymeric Conductors

383

(2)

7.1.3 Molecular Assemblies; Polymers Constructed with Metal-containing Macrocycles

385

(2)

7.1.4 Techniques for the Characterisation of Polymeric and Molecular Conductors

387

(4)

7.2 Examples of Polymeric Systems

391

(17)

7.2.1 Polymers Constructed with Non-Covalent Bridging Ligands

391

(1)

7.2.2 Polymers Constructed with Covalent Linkages

392

(16)

7.3 Electrochemical Characterisation of Soluble Polymeric Coordination Complexes

408

(10)

7.3.1 Homogeneous Electrochemical Doping

408

(6)

7.3.2 Digital Simulations of Voltammetric Results

414

(1)

7.3.3 Following Chemical Stability as a Function of the Degree of Band-Filling by Voltammetric Techniques

414

(2)

7.3.4 Correlations Between Electronic Structure and Voltammetric Response

416

(2)

7.4 Summary and Outlook

418

(1)

7.5 Acknowledgements

419

(1)

7.6 References

419

(10)

8 Metal-containing Liquid Crystals

429

(94)

Duncan W Bruce

8.1 Introduction

433

(1)

8.2 The Thermotropic Liquid Crystal State

434

(10)

8.2.1 Calamitic Mesophases

434

(5)

8.2.2 Columnar Mesophases

439

(1)

8.2.3 The Chemical Nature of Thermotropic Mesogens

440

(2)

8.2.4 Physical Properties of Thermotropic Liquid Crystals

442

(2)

8.3 Lyotropic Liquid Crystals

444

(2)

8.4 Mesophase Characterisation

446

(3)

8.4.1 Polarised Optical Microscopy

446

(2)

8.4.2 Differential Scanning Calorimetry

448

(1)

8.4.3 Small-angle X-ray Scattering

448

(1)

8.5 Metal Complexes as Liquid Crystals

449

(2)

8.5.1 Historical Perspective

450

(1)

8.6 Mesomorphic Coordination Complexes of Monodentate Ligands

451

(14)

8.6.1 Complexes of Organonitriles

451

(1)

8.6.2 Complexes of Organoisonitriles

452

(3)

8.6.3 Complexes of Substituted Pyridines

455

(7)

8.6.4 Acetylide Complexes

462

(2)

8.6.5 Thiolate Complexes

464

(1)

8.6.6 Physical Properties of Complexes of Monodentate Ligands

464

(1)

8.7 Mesomorphic Coordination Complexes of Bidentate Ligands

465

(35)

8.7.1 Dithiolene Complexes

465

(1)

8.7.2 Dithiolene Complexes with Four and Eight chains

466

(1)

8.7.3 Dithiobenzoates

467

(4)

8.7.4 Dithiocarbamate Complexes

471

(1)

8.7.5 Physical Properties of Mesogens with Bidentate Sulphur Ligands

471

(1)

8.7.6 Complexes with N, O Donor Sets and Four Terminal Chains

472

(8)

8.7.7 Ortho-metallated Palladium and Platinum Complexes

480

(7)

8.7.8 Large, Macrocyclic, Orthometallated Complexes

487

(1)

8.7.9 Other Orthometallated Complexes

488

(1)

8.7.10 Complexes of β-Diketonates with Two or Four Terminal Chains

489

(6)

8.7.11 Complexes of β-Diketonates with Eight or More Terminal Chains

495

(2)

8.7.12 Dinuclear Complexes of Alkanoic Acids with Four Peripheral Chains

497

(100)

8.7.13 Complexes of α-Diimine Ligands

597

8.8 Mesomorphic Coordination Complexes of Polydentate Ligands

500

(7)

8.8.1 Metallophthalocyanines

500

(4)

8.8.2 Metalloporphyrins

504

(1)

8.8.3 Macrocyclic Systems

505

(1)

8.8.4 Poly(oxo) Systems

506

(1)

8.9 Organoiron Liquid Crystals

507

(3)

8.9.1 Ferrocenes

507

(2)

8.9.2 Iron Tricarbonyl Derivatives

509

(1)

8.10 Lyotropic Liquid Crystals

510

(3)

8.11 Where Lies the Future?

513

(1)

8.12 Acknowledgements

513

(1)

8.13 References

513

(10)

9 Precursors for Electronic Materials

523

(50)

Paul O'Brien

9.1 Electronic Materials

525

(4)

9.1.1 Semiconductors

525

(2)

9.1.2 p-n Junctions

527

(1)

9.1.3 Other Materials

528

(1)

9.2 Methods for Crystal Growth

529

(5)

9.2.1 MOCVD and Related Methods

530

(3)

9.2.2 Other Chemical Deposition Methods

533

(1)

9.3 Requirements for Precursors

534

(3)

9.3.1 Classes of Molecules Used as Precursors

534

(1)

9.3.2 Metal Alkyls and Adduct Purification

535

(1)

9.3.3 The Preparation of High-purity Alkyls

536

(1)

9.4 Precursors for IIVV Materials

537

(5)

9.4.1 III/V Semiconductors

537

(1)

9.4.2 Group 13 Precursors

538

(2)

9.4.3 Alternative Group 15 Precursors

540

(1)

9.4.4 Single-molecule precursors

540

(2)

9.5 Precursors for II/VI Materials

542

(9)

9.5.1 II/VI Materials

542

(1)

9.5.2 Metal Precursors for II-VI Deposition

542

(2)

9.5.3 Nature of the Effect of Adducts on Growth

544

(4)

9.5.4 Alternative Group 16 Sources

548

(1)

9.5.5 Single-molecule Precursors

548

(3)

9.6 Precursors for Oxides

551

(6)

9.6.1 High Tc Superconductors

551

(3)

9.6.2 Other Oxides

554

(3)

9.7 Other Materials Important in Semiconductor Fabrication

557

(3)

9.7.1 Metallisation

557

(3)

9.7.2 Silicides

560

(1)

9.8 Update

560

(4)

9.8.1 Compound Semiconductors

560

(1)

9.8.2 Oxides

561

(1)

9.8.3 Metallisation

561

(1)

9.8.4 Nanodispersed Electronic Materials

561

(3)

9.9 Acknowledgements

564

(1)

9.10 References

564

(9)

Subject Index

573

(16)

Compound Index

589

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Inorganic Materials

Summary

Author Biography

Table of Contents

Supplemental Materials

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Inorganic Materials

Summary

Author Biography

Table of Contents

Supplemental Materials

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