Chemistry of Polymeric Metal Chelates (eBook)

Preface 7
Contents 9
About the Authors 15
Acronyms 17
1 General Introduction 24
Abstract 24
References 32
2 Polymer Chelating Ligands: Classification, Synthesis, Structure, and Chemical Transformations 36
Abstract 36
2.1 Linear, Branched and Network Polymers as Chelating Macroligands 38
2.1.1 (Co)polymerization of Chelating Monomers 39
2.1.2 Chelating Macroligands Obtained by the Methods of Controlled Radical Polymerization 43
2.1.3 ROMP as a Method of Production of Chelating Polymers 48
2.1.4 Click Chemistry Methods in Synthesis of Chelating Polymers 50
2.1.5 Method of Cation Polymerization in Chemistry of Chelating Macroligands 51
2.1.6 Chemical Oxidized Polymerization in the Chemistry of Chelating Polymers 52
2.1.7 Chelating Macroligands Obtained by the Methods of Photo- and Microwave-Assisted Polymerization 54
2.1.8 Cyclopolymerization for the Production of Chelating Macroligands 55
2.1.9 Asymmetrical Polymerization in Synthesis of Chelating Polymers 56
2.1.10 Chelating Macroligand Preparation via Post-polymerization Modification 59
2.1.11 Polycondensation Reactions as a Way to Chelating Polymers 62
2.1.12 «Green» Synthesis of Chelating Macroligands 64
2.2 Grafted Polymerization in Chelation of Macroligands 69
2.2.1 Specifics of Grafted Polymerization 69
2.2.2 Controlled Grafted Polymerization 74
2.2.3 Macromolecular «Brushes» 83
2.3 Dendrimers as Polymer Chelating Ligands 90
2.3.1 General Characteristics of Dendrimers 90
2.3.2 The Main Types of Chelating Dendrimers 93
2.3.3 Divergent and Convergent Synthesis 103
2.3.4 Alternative Methods of Synthesis 106
2.3.5 Using the Click Chemistry in the Synthesis of Dendrimers 109
2.3.6 The Post-synthetic Modification of Dendrimers 111
2.3.7 Fixing Dendrimers on Solid Surfaces 115
2.3.8 Properties of Chelating Dendrimers 115
2.4 Chelating Hyperbranched Polymers 117
2.4.1 Star Polymers 119
2.4.2 Methods of Synthesis of Hyperbranched Polymers 121
2.4.3 Post-synthetic Modification of Hyperbranched Polymers 132
2.5 Polymeric Films as Chelating Macroligands 136
2.5.1 Polymeric Films Based on Pre-formed Chelating Macroligands 137
2.5.2 Assembly of Polymeric Films from Chelating Monomers 141
2.5.3 Chemical Modification of Polymeric Films 152
2.6 Liquid Crystal Chelating Polymers 154
2.6.1 Polycondensation in the Synthesis of Liquid Crystal Polymers 156
2.6.2 Liquid Crystal Polymers Obtained by (Co)polymerization 162
2.6.3 Liquid Crystal Dendrimers and Hyperbranched Polymers 166
References 193
3 Metal Complexes with Polymer Chelating Ligands 221
Abstract 221
3.1 Molecular Metal Chelates 223
3.1.1 Chelation with Polyamine Ligands 223
3.1.2 Metal Chelates Based on Schiff Bases 230
3.1.3 Polymeric Five-Membered Nitrogenous Heterocycles in the Synthesis of Metal Chelates 233
3.1.4 Specifics of Metal Chelation with Polypyridyl Ligands 239
3.1.5 Metal Chelates Formed by N,O-Containing Ligands 271
3.1.6 Binding of Metal Compounds with O,O-Containing Ligands 272
3.1.7 Metal Chelates with N,S-Containing Ligands 273
3.1.8 Some Examples of Metal Chelates with P-Containing Ligands 278
3.2 Intracomplex Compounds 279
3.2.1 Chelation with Polyphenol Ligands 279
3.2.2 ?-Diketonates 284
3.2.3 Metal Chelates of Salicylaldehyde Type Ligands 285
3.2.4 Metal Chelates Based on Salicylic Acid Containing Polymers 287
3.2.5 Features of Metal Chelation with Spyropyran-Containing Ligands 291
3.2.6 Metal Chelates with Anthranilic Acid 292
3.2.7 Polymeric o-Aminophenol and Its Derivatives in the Synthesis of Metal Chelates 294
3.2.8 Specifics of Metal Chelation with Schiff Bases 296
3.2.9 Salen and Salphen Types of Metal Chelates 307
3.2.10 8-Hydroxyquinoline Type of Metal Chelates 318
3.2.11 Metal Chelates with Amidoxime and Hydroxamic Acid 323
3.2.12 Metal Ion Binding with Aminopolycarboxylic Acids 325
3.2.12.1 Iminodiacetic Acid 325
3.2.12.2 Nitrilotriacetic Acid 331
3.2.12.3 Ethylenediaminetetraacetic Acid 331
3.2.12.4 Diethylenetriamine Pentacetic Acid 332
3.2.13 Metal Chelates with Other N,O-Containing Ligands 337
3.2.14 Chelation with N,S-Containing Ligands 343
3.2.15 Metal Chelates Based on S,S-Containing Ligands 347
3.3 Macrocyclic Complexes 350
3.3.1 Preparation of Metal Chelates with Participation of Cyclam-Containing Polymers 350
3.3.2 Metal Chelates with Cyclen-Containing Polymers 351
3.3.3 Specifics of Chelation with DOTA and Related Ligands 352
3.3.4 Metal Chelates Based on Polymeric Podands 356
3.3.5 Metal Chelates with Triolefinic Azamacrocycle 357
3.3.6 Porphyrin and Phthalocyanine Complexes 358
3.3.7 Metal Complexes Based on Crown Ethers 360
3.3.8 Polymeric Azacrown Ethers as Chelating Ligands 366
3.3.9 Metal Complexes with Thiacrown Ethers 368
3.3.10 Calix[4]pyrrole[2]thiophene as Chelating Ligands 370
3.4 Polynuclear Polymeric Metal Chelates 371
References 374
4 Polymer Complexes Based on Metal Chelate Monomers 389
Abstract 389
4.1 Homopolymerization 390
4.2 Copolymerization 395
4.3 Living and Controlled Polymerization 405
4.4 Electropolymerization 416
4.5 Grafted Polymerization 432
4.6 Polycondensation 434
4.7 Synthesis of Dendrimers and Hyperbranched Polymers Based on Metal Chelate Monomers 461
References 510
5 Metal Chelate Dendrimers 524
Abstract 524
5.1 Molecular Metal Chelates 526
5.1.1 Metal Chelates with N-Donor Ligands 526
5.1.2 N,P-Ligands 547
5.1.3 Metal Chelates with P,S-Ligands 549
5.1.4 Metal Chelates with P,P-Ligands 549
5.1.5 Pincer Complexes 557
5.1.6 Chelating Dendrimers as Metal Sensors 558
5.2 Intracomplex Compounds 561
5.2.1 Salen-Type Chelates 562
5.2.2 8-Hydroxyquinoline Chelates 569
5.2.3 Pyrrolide-Imine Chelates 569
5.2.4 O,O-Chelates 570
5.2.5 S,O-Chelates 571
5.2.6 P,O-Chelates 572
5.2.7 Metal Chelates with Polydentate Ligands 572
5.3 Macrocyclic Complexes 577
5.3.1 Metal Complexes with Pseudo-crown Ethers and Crown Ethers 577
5.3.2 Metal Complexes with Cyclam-Containing Dendrimers 581
5.3.3 Metal Complexes with Cyclen-Containing Dendrimers 583
5.3.4 Metal Chelates Based on Dendrimers with Triazacyclononane Fragments 584
5.3.5 Tetrapyrazinoporphyrazine Complexes 584
5.3.6 Porphyrin Complexes 585
5.3.7 Phthalocyanine Complexes 587
5.3.8 Metal Chelates with DOTA and Related Ligands 589
5.4 Metal Chelate Star Polymers 594
5.4.1 «Arm-First» Method 595
5.4.2 «Core-First» Method 606
5.4.3 Click-to-Chelate Approach 618
5.5 Metal Chelates with Hyperbranched Polymers 621
References 640
6 Coordination Polymers Containing Metal Chelate Units 653
Abstract 653
6.1 Crystal Engineering of Coordination Polymers 656
6.2 Reticular Chemistry 658
6.3 Metalloligand Strategy 661
6.4 Pillar-Layered Strategy 679
6.5 Approach Based on Supramolecular Building Blocks 684
6.6 Approach Based on Supramolecular Building Layers 686
6.7 Conventional Synthesis 690
6.7.1 Solvent Evaporation Method 692
6.7.2 Diffusion Methods 699
6.7.3 Hydro(Solvo)Thermal Methods 703
6.7.4 Urothermal Synthesis 728
6.7.5 Ionothermal Synthesis 728
6.7.6 Microfluidic Synthesis 729
6.7.7 Synthesis in Supercritical CO2 730
6.7.8 Surfactant-Thermal Method 731
6.7.9 In Situ Spacer Synthesis 732
6.8 Alternative Synthesis Routes 734
6.8.1 Microwave-Assisted Synthesis 735
6.8.2 Electrochemical Synthesis 737
6.8.3 Mechanochemical Synthesis 738
6.8.4 Sonochemical Synthesis 739
6.9 Post-synthetic Approaches 741
6.9.1 Post-synthetic Modification 742
6.9.2 Post-synthetic Deprotection 750
6.9.3 Post-synthetic Exchange 751
References 759
7 Supramolecular Chemistry of Polymer Metal Chelates 780
Abstract 780
7.1 Supramolecular Polymers 782
7.2 Metallosupramolecular Polymerization 785
7.3 Linear Metallosupramolecular Polymers 789
7.4 Branched Metallosupramolecular Polymers 807
7.5 Cross-Linked Metallosupramolecular Polymers 811
7.6 Heterometallic Supramolecular Polymers 815
7.7 Metallosupramolecular Polyelectrolytes 818
7.8 Orthogonal Self-assembling 822
7.8.1 Combination of M–L Coordination with H-Bonding Interactions 824
7.8.2 Combination of M–L Coordination with Host-Guest Interaction 828
7.9 Hierarchical Self-assembling 838
7.10 Metallosupramolecular Polymer Gels 844
7.11 Self-assembled Metallosupramolecular Monolayers 861
7.12 Supramolecular Metal Chelate Dendrimers 871
7.13 Stimuli-Responsive Metallosupramolecular Polymers 883
7.14 Self-healing and Shape-Memory Metallosupramolecular Polymers 893
References 899
8 Thermal Transformations of Polymeric Metal Chelates and Their Precursors in Nanocomposites Formation 917
Abstract 917
8.1 Thermolysis Methods of Polymeric Metal Chelates 918
8.1.1 Thermogravimetric Methods 918
8.1.2 Linear Pyrolysis Method 919
8.1.3 Volumetric Methods 919
8.1.4 Thermolysis Induced by High-Energy Radiation 920
8.1.5 Spray Pyrolysis 920
8.1.6 Chemical Vapor Deposition 921
8.2 Metal Chelates As «Single-Source» Precursors of Nanocomposites 921
8.2.1 Chalcogenide Metal Chelates 925
8.2.1.1 Influence of the Ligand Nature 926
8.2.1.2 Environment Influence 929
8.2.1.3 Temperature Influence 933
8.2.2 Controlled Thermolysis of Azomethine Transition Metal Chelates 936
8.2.2.1 Nickel(II) Chelates 942
8.2.2.2 Copper(II) Chelates 945
8.2.2.3 Cobalt(II) Chelates 945
8.2.2.4 Composition and Structure of Thermolysis Products of Azomethine Metal Chelates 946
8.2.3 Metal Chelate Thermolysis in Polymer Matrix 949
8.3 The Conjugate Thermolysis—Nanoparticle and Polymer Matrix Formation Process 952
8.3.1 Thermolysis Kinetics of Metal Carboxylates 954
8.3.2 Key Temperature-Separation Stages of Thermal Transformations of Metal Carboxylates 955
8.3.2.1 Dehydration 956
8.3.2.2 Polymerization 957
8.3.2.3 Decarboxylation 958
8.3.3 The Composition of the Gaseous and Solid Thermolysis Products of Metal-Containing Monomers 968
8.3.3.1 The Gaseous and Condensed Products 968
8.3.3.2 The Composition of the Solid-Phase Products 969
8.3.4 Kinetic Schemes and Thermal Transformation Reactions of Metal-Containing Monomers 973
8.3.4.1 The Total Kinetic Scheme and the Decomposition Pathways of the Metal-Containing Monomers 973
8.3.4.2 Transformation Pathways of Cobalt Acrylate 975
8.4 Thermolysis of Polymeric Metal Chelates 984
8.4.1 Synthesis of Carbon Materials 986
8.4.2 The Preparation of Metal Oxide Materials 995
8.4.2.1 Influence of the Original Morphology and Particle Size of Polymeric Metal Chelates 997
8.4.2.2 Influence of Temperature 1003
8.4.2.3 Influence of Surfactants 1005
8.4.3 Polymer Derived Non-oxide Nanocomposites 1006
8.4.4 Mixed-Oxide Nanocomposites 1008
References 1014
Conclusions and Future Prospects 1026
Index 1029