Smart Inorganic Polymers
Synthesis, Properties, and Emerging Applications in Materials and Life Sciences

Provides complete and undiluted knowledge on making inorganic polymers functional.

This comprehensive book reflects the state of the art in the field of inorganic polymers, based on research conducted by a number of internationally leading research groups working in this area. It covers the synthesis aspects of synthetic inorganic polymers and looks at multiple inorganic monomers as building blocks, which exhibit unprecedented electronic, redox, photo-emissive, magnetic, self-healing and catalytic properties. It also looks at the applications of inorganic polymers in areas such as optoelectronics, energy storage, industrial chemistry, and biology.

Beginning with an overview of the use of smart inorganic polymers in daily life, Smart Inorganic Polymers: Synthesis, Properties and Emerging Applications in Materials and Life Sciences goes on to study the synthesis, properties, and applications of polymers incorporating different heteroelements such as boron, phosphorus, silicon, germanium, and tin. The book also examines inorganic polymers in flame-retardants, as functional materials, and in biology.

• An excellent addition to the polymer scientists' and synthetic chemists' toolbox
• Summarizes the state of the art on how to make and use functional inorganic polymers, from synthesis to applications
• Edited by the coordinator of a highly funded European community research program (COST action) that focuses specifically on the exploration of inorganic polymers
• Features contributions from top experts in the field

Aimed at academics and industrial researchers in this field, Smart Inorganic Polymers: Synthesis, Properties and Emerging Applications in Materials and Life Sciences will also benefit scientists who want to get a better overview on the state-of-the-art of this rapidly advancing area.

Preface xi

1 Current Status and Future Perspectives of Functional and Smart Materials in Daily Life 1
Rudolf Pietschnig

1.1 Introduction 1

1.2 Properties and Applications 1

1.2.1 Applications Based on Mechanical and Rheological Properties 1

1.2.2 Applications Based on Electronic Excitation 2

1.2.3 Applications Based on Optical Features 6

1.2.4 Applications Based on Supramolecular Recognition 9

1.2.5 Applications Based on Chemical Reactivity 10

1.2.6 Further Applications 12

1.3 Perspective 13

Acknowledgments 13

References 13

2 Boron-Containing Polymers 17

2.1Group 13–Group 15 Element Bonds Replacing Carbon–Carbon Bonds in Main Group Polyolefin Analogs 19
Anne Staubitz, Jonas Hoffmann, and Philipp Gliese

2.1.1 Introduction 19

2.1.2 Group 13–Group 15 Element-Containing Polyolefin Analogs with the Heteroatoms in the Main Chain 20

2.1.2.1 Poly(phosphinoboranes) 20

2.1.2.1.1 Metal Complexes as Catalysts for the Dehydrocoupling of Phosphine–Boranes 21

2.1.2.1.2 Lewis Acid Promoted Dehydrocoupling of Phosphine–Boranes 23

2.1.2.1.3 Lewis Base Promoted Dehydrocoupling of Phosphine–Boranes 24

2.1.2.1.4 Poly(phosphinoborane)-Based Materials 25

2.1.2.1.5 Potenial Applications of Poly(phosphinoboranes) 25

2.1.2.2 Poly(aminoboranes) 27

2.1.3 Group 13–Group 15 Element-Containing Polyolefin Analogs with the Heteroatoms in the Side Chain 32

2.1.3.1 Borazine-Containing PS Analogs 32

2.1.3.2 Azaborinine-Containing PS Analogs 33

2.1.4 Conclusion and Outlook 35

Acknowledgments 36

References 36

2.2 Highlighting the Binding Behavior of Icosahedral Boron Clusters Incorporated into Polymers: Synthons, Polymers Preparation, and Relevant Properties 41
Clara Viñas, Rosario Núñez, Isabel Romero, and Francesc Teixidor

2.2.1 Introduction 41

2.2.2 Conducting Organic Polymers Containing Icosahedral Boron Clusters 42

2.2.2.1 Icosahedral Boron Clusters as Doping Agents in COPs 43

2.2.2.2 Icosahedral Boron Clusters in COPs Side Chains to Modify the Chemical Composition and Act as Doping Agent 44

2.2.2.3 Icosahedral Boron Clusters Incorporated into the Polymer Main Chain of the COPs 45

2.2.3 Fluorescent Carborane-Containing Polymers 46

2.2.4 Thermally Resistant Carborane-Based Polymers 48

2.2.5 Coordination Polymers and Nanoparticles Incorporating closo-Carborane Clusters 50

2.2.5.1 Carboxylate-Functionalized Carboranes 50

2.2.5.2 Phosphinate- and Phosphino-Functionalized Carboranes 51

2.2.5.3 Nanohybrid Materials Based on Functionalized Carboranes 52

2.2.6 Conclusion and Outlook 55

Acknowledgments 55

References 55

3 Synthesis of Group 14 Metal-Containing Polymers 61
Ana Torvisco, Frank Uhlig, and David Scheschkewitz

3.1 Introduction 61

3.2 Organohydrides of Group 14, RnEH_4−n 62

3.3 Diorganodihydrides of Group 14, R2EH₂, as Building Blocks for Chain-Type Polymers 65

3.3.1 Metal-Catalyzed Dehydropolymerization 65

3.3.2 Dehydrogenative Coupling Using an Amine Base 65

3.3.3 Solvent- and Catalyst-Free Dehydrogenative Coupling 67

3.3.4 Condensation 68

3.4 Monoorganotrihydrides of Group 14, REH₃, as Building Blocks for 3D Polymers 68

3.4.1 Metal-Catalyzed Dehydropolymerization 68

3.4.2 Dehydrogenative Coupling Using an Amine Base 69

3.5 Applications 72

3.6 Conclusion and Outlook 74

Acknowledgments 75

References 75

4 Synthesis of Polymers Containing Group 15 Elements 85
Andreas Orthaber and Alejandro P. Soto

4.1 Introduction 85

4.2 Conjugated Polymers Containing Group 15 Elements 86

4.2.1 Phosphaalkenes, Arsaalkenes, and Diphosphenes 86

4.2.2 Group 15-Based Heteroles 89

4.3 Polymers with two Unsaturated Organic Moieties Adjacent to the Heteroelement Motif 93

4.3.1 Cross-Conjugated Group 15 Heteroalkene-ContainingMaterials 93

4.3.2 Group 15 Elements with two Adjacent Alkynes, Alkenes, or Arene Motifs of the Polymer Backbone 94

4.3.2.1 Ring-Opening Polymerization 95

4.4 Organic–Inorganic Hybrid Polymers Containing Saturated Phosphorus Centers 96

4.4.1 Miscellaneous Polymers 97

4.5 Polyphosphazene 97

4.6 Poly(phosphoester)s 104

4.7 Conclusion and Outlook 107

Acknowledgments 107

References 107

5 Synthesis of Inorganic Dendrimers 115
Anne-Marie Caminade

5.1 Introduction 115

5.2 Main Methods of Synthesis of Silicon-Containing Dendrimers 115

5.2.1 Synthesis of Carbosilane Dendrimers 115

5.2.2 Synthesis of Other Types of Silicon-Containing Dendrimers 118

5.3 Main Methods of Synthesis of Phosphorus-Containing Dendrimers 120

5.3.1 Synthesis of Phosphorhydrazone Dendrimers 120

5.3.2 Synthesis of Other Types of Phosphorus-Containing Dendrimers 121

5.4 Synthesis of Miscellaneous Types of Inorganic Dendrimers 129

5.4.1 Synthesis of Dendrimers ContainingMain Group Elements Other than Si and P 129

5.4.2 Synthesis of Hybrid Dendrimers Containing at Least Two Types of Main Group Elements 132

5.5 Conclusion and Outlook 135

Acknowledgments 135

References 136

6 Metallo-Supramolecular Polymers 141
Jirí Vohlídal and Muriel Hissler

6.1 Introduction 141

6.2 Constitutional Dynamic Polymers: Dynamers 142

6.3 Main Types of Metallo-Supramolecular Polymers (MSPs) and Terminologies Related to Them 143

6.4 MSP Dynamers Derived from Unimers with Defined Structure 144

6.4.1 Synthesis of Unimers 144

6.4.2 Central Blocks of Conjugated Unimers 146

6.4.3 Assembly and Characterization of MSP Dynamers 148

6.4.4 Properties of Conjugated MSPs 151

6.5 Potential Applications and Outlook 155

6.5.1 Electrochromic Devices Based on the Modification of the Absorption Properties 155

6.5.2 Electrochromic Devices Based on the Modification of the Emission Properties 156

6.5.3 Ion Conductivity 157

6.5.4 Actuators 157

6.5.5 Outlooks 157

Acknowledgments 158

References 158

7 Applications of Heteroatom-Based Oligomers and Polymers in Optoelectronics 163
Matthew P. Duffy, Pierre-Antoine Bouit, and Muriel Hissler

7.1 Introduction 163

7.2 Organic Light-Emitting Diodes (OLEDs) 164

7.2.1 Application as Charge-Transport Layer 166

7.2.2 Application as Host for Phosphorescent Complexes 169

7.2.3 Application as Emitting Materials 171

7.3 Photovoltaic Cells (Organic Solar Cells [OSCs] and Dye-Sensitized Solar Cells [DSSCs]) 181

7.3.1 Dyes for Dye-Sensitized Solar Cells (DSSCs) 183

7.3.2 Donors in Organic Solar Cells (OSCs) 184

7.4 Application in Electrochromic Cells 188

7.5 Conclusion 189

Acknowledgments 189

Abbreviations 190

References 192

8 Inorganic Polymers as Flame-Retardant Materials 197
Raghvendra KumarMishra, Tarik Eren, and De-YiWang

8.1 Introduction 197

8.2 Importance of Flame-Retardant Materials 198

8.3 Application of Inorganic Polymer as a Flame-Retardant Material 200

8.3.1 Polysiloxanes 201

8.3.2 Polyphosphazenes 210

8.3.3 Polysilane and Polysilynes 220

8.3.4 Ferrocene-Based Polymers 222

8.3.5 Carborane-Containing Polymers 225

8.3.5.1 Poly(carboranylenesiloxanes) 226

8.3.5.2 Carborane-Containing High-Performance Thermoplastics 229

8.3.5.3 Carboranes as Miscellaneous Polymers 230

8.4 Conclusion 233

Acknowledgments 233

References 233

9 Inorganic Polymers for Potential Medicinal Applications 243
Andreia Valente, Rafaella L. M. Precker, and Evamarie Hey-Hawkins

9.1 Introduction 243

9.2 Inorganic Polymers and Metal-Containing Polymers for Tissue Engineering and Drug Delivery 243

9.2.1 Inorganic Polymers 243

9.2.1.1 Polysiloxanes 244

9.2.1.2 Polyphosphazenes 247

9.2.2 Metal-Containing Polymers 250

9.2.2.1 Platinum–Polymer Conjugates 251

9.2.2.2 Ruthenium–Polymer Conjugates 251

9.2.2.3 Carborane–Polymer Conjugates 254

9.3 Emerging and Potential Applications for Metal-Organic Frameworks for Drug Delivery 255

9.3.1 Metal-Organic Frameworks (MOFs) 257

9.3.2 Application of MOFs in Drug Delivery Systems 257

9.3.2.1 Selected Examples of MIL-n Frameworks in Drug Delivery 258

9.3.2.2 Selected Other Metal-Organic Frameworks Used in Drug Delivery 262

9.3.3 Toxicity and Stability 263

9.3.3.1 Toxicity 263

9.3.3.2 Stability 265

9.3.4 Biodegradation 265

9.4 Final Remarks and Perspectives 266

Acknowledgments 267

References 267

10 Inorganic Dendrimers and Their Applications 277
Anne-Marie Caminade

10.1 Introduction 277

10.2 Inorganic Dendrimers as Catalysts 278

10.2.1 Overview of the Use of Inorganic Dendrimers as Catalysts 278

10.2.2 The Dendrimer Effect Illustrated with Catalytic Inorganic Dendrimers 280

10.2.3 The Recovery and Reuse of Catalytic Inorganic Dendrimers 283

10.3 Inorganic Dendrimers for Nanomaterials 287

10.3.1 Elaboration of Materials and Nano-objects Exclusively Composed of Inorganic Dendrimers 288

10.3.2 Hybrid Materials Incorporating Inorganic Dendrimers 291

10.3.3 Modification of the Surface of Materials with Inorganic Dendrimers Toward Biological Uses 293

10.4 Inorganic Dendrimers in Biology/Nanomedicine 296

10.4.1 Inorganic Dendrimers for Bioimaging 296

10.4.2 Inorganic Dendrimers for Gene Therapy 298

10.4.3 Inorganic Dendrimers Against Viruses 299

10.4.4 Inorganic Dendrimers in Brain Diseases 301

10.4.5 Inorganic Dendrimers Against Cancers 301

10.4.6 Inorganic Dendrimers Against Inflammatory Diseases 302

10.5 Conclusion and Outlook 304

Acknowledgments 304

References 305

11 Other Examples of Inorganic Polymers as Functional Materials 317
IreneWeymuth and Walter Caseri

11.1 Introduction 317

11.1.1 1,2,4-Triazole in Coordination Chemistry 317

11.1.2 Spin-Crossover 319

11.2 Coordination Polymers of 4-Aminotriazole and Iron(II) 322

11.2.1 Solutions 322

11.2.2 Solid State 324

11.3 Coordination Polymers of 4-Alkyltriazoles and Iron(II) 327

11.4 Coordination Polymers of 1,2,4-Triazoles and Other Metals 330

11.5 Conclusion and Outlook 332

Acknowledgments 333

References 333

Index 337

Evamarie Hey-Hawkins is Full Professor and holds a Chair of Inorganic Chemistry at Leipzig University, Germany. Her broad research interests include biological and medicinal chemistry, homogeneous catalysis with transition metal complexes, and precursors for novel materials. She was Chair of the COST Action CM1302, the European Network on Smart Inorganic Polymers (SIPs), and has received numerous awards from international chemical societies and the Order of Merit of the Free State of Saxony, Germany, in May 2017.

Muriel Hissleris Full Professor of Chemistry at the Institute of Chemical Sciences of the University of Rennes, France. Her research activities are mainly directed towards the synthesis of heteroatom-based pi-conjugated oligomers or polymers having physical properties useful for optoelectronic applications. She was Vice Chair and Short Term Scientific Missions (STSM) coordinator within the COST Action CM1302. She received the prize of the Division of Coordination Chemistry of the French Chemical Society and she is a member of the Institut Universitaire de France.