Main Group Metal Coordination Polymers: Structures and Nanostructures

This first–ever book to discuss metal coordination chemistry at the nano scale informs researchers and graduate students how to understand metal coordination polymers in bulk and nano dimensions and their applications.

Coordination polymer is a general term used to indicate an infinite array composed of metal ions which are bridged by certain ligands among them. This incorporates a wide range of architectures including simple one–dimensional chains with small ligands to large mesoporous frameworks. Generally, the formation process proceeds automatically and, therefore, is called a self–assembly process. In general, the type and topology of the product generated from the self–assembly of inorganic metal nodes and organic spacers depend on the functionality of the ligand and valences and the geometric needs of the metal ions used.

In this book the authors explain main group metal coordination polymer in bulk and nano size with some of their application, synthesis method, etc, The properties of these efficient materials are described at length including magnetism (long–range ordering, spin crossover), porosity (gas storage, ion and guest exchange), non–linear optical activity, chiral networks, reactive networks, heterogeneous catalysis, luminescence, multifunctional materials and other properties.

Audience
The core audience of this book is inorganic chemists working in the field of coordination chemistry, coordination polymers and metal organic frameworks, as well as nanotechnologists. PhD and master students will find the book extremely valuable.

Preface xi

1 Introduction to Coordination Polymers 1

1.1 Coordination Space 1

1.2 Coordination Polymer 3

1.3 Development of Coordination Polymer 7

1.4 Synthetic Methods 9

1.5 Design of Coordination Polymer 13

References 18

2 Application of Coordination Polymers 23

2.1 Introduction 23

2.2 Gas Storage 24

2.3 Catalysis 26

2.4 Luminescence 28

2.5 Redox Activity 29

2.6 Magnetism 29

2.6.1 Long–range Magnetic Ordering 29

2.6.1.1 Molecule–based Magnets 32

2.6.1.2 Single–chain Magnets 33

2.6.2 Spin Crossover 33

2.7 Acentric and Chiral Networks 35

References 39

3 Zinc(II) Coordination Polymers 43

3.1 Introduction to Zinc(II) Coordination Polymers 43

3.1.1 Coordination Polymers Constructed from Rigid Two–connecting Ligands 45

3.1.1.1 Rod–type Ligands 45

3.1.1.2 Angular, Rigid Two–connectors 49

3.1.2 Coordination Polymers Constructed from Rigid, Trigonal Three–connectors 52

3.1.3 Coordination Polymers Constructed from Carboxylates, Pyridine Carboxylates and Pyrazine Carboxylates 54

3.1.4 Coordination Polymers Constructed from Secondary Building Blocks (SBUs) 57

3.1.5 Coordination Polymers Constructed from Conformational Flexible Ligands 59

3.1.6 Coordination Polymers Constructed from

Phosphate and Phosphonate Ligands 63

3.2 Nano Zinc(II) Coordination Polymers 64

3.3 Conclusion 70

References 71

4 Cadmium(II) Coordination Polymers 81

4.1 Introduction to Cadmium (II) Coordination Polymers 81

4.1.1 One–dimensional Coordination Polymers 82

4.1.2 Two–dimensional Coordination Polymers 86

4.1.3 Three–dimensional Coordination Polymers 93

4.2 Nano Cadmium(II) Coordination Polymers 96

4.3 Conclusion 102

References 103

5 Mercury(II) Coordination Polymers 113

5.1 Introduction Mercury(II) Coordination Polymers 113

5.1.1 One–dimensional Coordination Polymers 115

5.1.2 Two–dimensional Coordination Polymers 120

5.1.3 Three–dimensional Coordination Polymers 124

5.2 Nano Mercury(II) Coordination Polymers 126

5.3 Conclusion 131

References 131

6 Lead(II) Coordination Polymers 137

6.1 Introduction 137

6.2 Mono–donor Coordination Mode 139

6.2.1 Discrete Complexes 139

6.2.2 One–dimensional Coordination Polymers 141

6.2.3 Two–dimensional Coordination Polymers 142

6.2.4 Three–dimensional Coordination Polymers 142

6.3 Bi–donor Coordination Polymers 143

6.3.1 Bridging ( 2 1: 1) Mode 143

6.3.1.1 Discrete Complexes 143

6.3.1.2 One–dimensional Coordination Polymers 144

6.3.1.3 Two–dimensional Coordination Polymers 144

6.3.1.4 Three–dimensional Coordination Polymers 145

6.4 Tri–donor Coordination Polymers 148

6.4.1 Bridging ( 3 1: 2) Mode 148

6.4.1.1 Two–dimensional Coordination Polymer 148

6.4.1.2 Three–dimensional Coordination Polymers 148

6.5 Tetra–donor Coordination 148

6.5.1 Chelating, Bridging ( 3 1: 2: 1) Mode 148

6.5.1.1 One–dimensional Coordination Polymers 150

6.5.1.2 Two–dimensional Coordination Polymers 151

6.5.1.3 Three–dimensional Coordination Polymers 152

6.6 Nano Lead(II) Coordination Polymers 152

6.7 Conclusion 164

References 165

7 Thallium(I) Coordination Polymers 177

7.1 Introduction to Thallium(I) Coordination Polymers 177

7.2 Thallium(I) Coordination Polymers 182

7.2.1 One–dimensional Coordination Polymers with Secondary Interactions in TlI Coordination Sphere 183

7.2.2 One–dimensional Coordination Polymers without Secondary Interactions in TlI Coordination Sphere 186

7.2.3 Two–dimensional Coordination Polymers with Secondary Interactions in TlI Coordination Sphere 187

7.2.4 Two–dimensional Coordination Polymers without Secondary Interactions in TlI Coordination Sphere 189

7.2.5 Three–dimensional Coordination Polymers with Secondary Interactions in TlI Coordination Sphere 190

7.2.6 Three–dimensional Coordination Polymers without Secondary Interactions in TlI Coordination Sphere 192

7.3 Nano Thallium(I) Coordination Polymers 193

7.4 Conclusion 198

References 199

8 Bismuth(III) Coordination Polymers 207

8.1 Introduction to Bismuth Coordination Polymers 207

8.2 Bismuth(III) Complexes with Monoaminopoly Carboxylate 211

8.2.1 Bi(III) Complexes with Iminodiacetate Ligands 211

8.2.2 Bi(III) Complexes with Nitrilotriacetate 212

8.2.3 Bi(III) Complexes with 2–hydroxy– ethyliminodiacetate 214

8.2.4 Bi(III) complexes with Pyridinedicarboxylate  Ligands 215

8.3 Bismuth(III) Complexes with Diaminopolycarboxylate Ligands 217

8.3.1 Bi(III) Complexes with Ethylenediaminetetraacetate 217

8.3.1.1 Protonated Bi(III) Ethylenediaminetetraacetate Complexes 217

8.3.1.2 Bi(III) Ethylenediaminetetraacetate Complexes with Alkali Metal and Ammonium Cations 218

8.3.1.3 Bi(III) Ethylenediaminetetraacetate Complexes with Divalent Metal Cations 221

8.3.1.4 Bi(III) Ethylenediaminetetraacetate Complexes with Protonated Organic Base Cations 222

8.3.1.5 Bi(III) Ethylenediaminetetraacetates with Metal Complex Cations 222

8.3.1.6 Mixed–ligand Bi(III) Ethylenediaminetetraacetate Complexes 224

8.3.2 Bi(III) Complexes with other than edta4 diaminopolycarboxylate Ligands 226

8.4 Bismuth Complexes with Polyaminopolycarboxylate Ligands 228

8.4.1 Bi(III) Complexes with Diethylenetriaminepentaacetate Ligands and its Analogues 228

8.4.2 Bi(III) Complexes with Triethylenetetraaminehexaacetate Ligands 229

8.4.3 Bi(III) Complexes with Macrocyclic Polyaminopolycarboxylate Ligands 231

8.5 Applications 232

8.6 Nano Bismuth(III) Coordination Polymers 232

8.7 Conclusion 238

References 240

9 Porous Main Group Coordination Polymers 247

References 270

10 S–block Coordination Polymers (Group1) 279

10.1 Introduction 279

10.2 Group 1(Alkali) Metal Coordination Polymers 280

10.2.1 Neutral Oxygen Donor Lligands 280

10.2.2 Anionic Oxygen Donor Ligands 283

10.2.2.1 Alkoxides and Aryloxides 283

10.2.2.2 Carboxylates 284

10.2.2.3 Sulfonates and Nitro–derivatives 284

10.2.2.4 Amino Acids 285

10.2.2.5 Mixed O– and N–donors 286

10.2.3 N–donor Ligands 287

10.2.4 Carbon Donor Ligands 288

10.2.5 Sulfur Donor Ligands 289

10.3 Conclusion 291

References 292

11 S–block Coordination Polymers (Group2) 297

11.1 Introduction 297

11.2 Group 2(Alkaline Earth) Metal Coordination Polymers 299

11.2.1 Neutral Oxygen Donor Ligands 300

11.2.2 Anionic Oxygen Donor Ligands 301

11.2.2.1 Beta–diketonates 301

11.2.2.2 Alkoxides 302

11.2.2.3 Carboxylates 302

11.2.2.4 Phosphonates 304

11.2.2.5 Sulfonates 305

11.2.3 Mixed N– and O–donors 305

11.2.4 N–donor Ligands 306

11.2.5 Carbon Donor Ligands 308

11.2.6 Sulfur Donor Ligands 309

11.3 Conclusion 310

References 311

Ali Morsali is Master in Inorganic Chemistry in Tarbiat Modares University, Tehran, Iran. He obtained his PhD in 2003 in Inorganic Chemistry from the same university. He has published more than 400 articles in international journals as well as 5 patents. He has received numerous national awards. Amongst his research interests are coordination chemistry and metal–organic frameworks.

Lida Hashemi is a postdoctoral researcher at Tarbiat Modarers University, Tehran, Iran. She obtained her PhD in inorganic chemistry from the same university in 2014. She has published 30 articles in international journals and has one patent to her name. Her research interests are coordination chemistry, nanotechnology and metal–organic frameworks.