Tailored Organic-Inorganic Materials

Ernesto Brunet, PhD, is Professor in the Department of Organic Chemistry at the Autonomous University of Madrid. Formerly a Fulbright and NATO Fellow with Prof. Ernest L. Eliel at the University of North Carolina, Chapel Hill, he has worked on numerous structural and stereochemical problems that led to his interest in the building of organic-inorganic materials where the organic moieties display unusual properties within the supramolecular architecture. Jorge L. Colón, PhD, is Professor in the Chemistry Department at the University of Puerto Rico. His research focuses on the use of layered inorganic materials in applications ranging from artificial photosynthesis, amperometric biosensors, vapochromic materials, and drug delivery systems. Abraham Clearfield, PhD, is Distinguished Professor at Texas A&M University. He received his BA and MA from Temple University in Philadelphia and his Ph.D. at Rutgers University in 1954. He has worked extensively on layered compounds, intercalation chemistry, inorganic ion exchangers including zeolites and metal phosphonate chemistry. He has published 560 papers in peer reviewed journals, edited four books and holds about 15 patents.

List of Contributors xi

Preface xiii

1 Zirconium Phosphate Nanoparticles and Their Extraordinary Properties 1

1.1 Introduction 1

1.2 Synthesis and Crystal Structure of α-Zirconium Phosphate 2

1.3 Zirconium Phosphate-Based Dialysis Process 5

1.4 ZrP Titration Curves 7

1.5 Applications of Ion-Exchange Processes 11

1.6 Nuclear Ion Separations 11

1.7 Major Uses of α-ZrP 12

1.8 Polymer Nanocomposites 12

1.9 More Details on α-ZrP: Surface Functionalization 17

1.10 Janus Particles 18

1.11 Catalysis 20

1.12 Catalysts Based on Sulphonated Zirconium Phenylphosphonates 22

1.13 Proton Conductivity and Fuel Cells 27

1.14 Gel Synthesis and Fuel Cell Membranes 30

1.15 Electron Transfer Reactions 32

1.16 Drug Delivery 34

1.17 Conclusions 39

References 40

2 Tales from the Unexpected: Chemistry at the Surface and Interlayer Space of Layered Organic–Inorganic Hybrid Materials Based on γ-Zirconium Phosphate 45

2.1 Introduction 45

2.2 The Inorganic Scaffold: γ-Zirconium Phosphate (Microwave-Assisted Synthesis) 46

2.3 Microwave-Assisted Synthesis of γ-ZrP 48

2.4 Reactions 51

2.4.1 Intercalation 51

2.4.2 Microwave-Assisted Intercalation into γ-ZrP 52

2.4.3 Phosphate/Phosphonate Topotactic Exchange 52

2.5 Labyrinth Materials: Applications 57

2.5.1 Recognition Management 57

2.5.1.1 Chirality at Play 62

2.5.1.2 Gas and Vapour Storage 69

2.5.2 Dissymmetry and Luminescence Signalling 71

2.5.3 Building DSSCs 75

2.5.4 Molecular Confinement 77

2.6 Conclusion and Prospects 78

References 79

3 Phosphonates in Matrices 83

3.1 Introduction: Phosphonic Acids as Versatile Molecules 83

3.2 Acid–Base Chemistry of Phosphonic Acids 84

3.3 Interactions between Metal Ions and Phosphonate Ligands 87

3.4 Phosphonates in ‘All-Organic’ Polymeric Salts 90

3.5 Phosphonates in Coordination Polymers 96

3.6 Phosphonate-Grafted Polymers 97

3.7 Polymers as Hosts for Phosphonates and Metal Phosphonates 108

3.8 Applications 113

3.8.1 Proton Conductivity 113

3.8.2 Metal Ion Absorption 117

3.8.3 Controlled Release of Phosphonate Pharmaceuticals 119

3.8.4 Corrosion Protection by Metal Phosphonate Coatings 125

3.8.5 Gas Storage 125

3.8.6 Intercalation 126

3.9 Conclusions 127

References 128

4 Hybrid Materials Based on Multifunctional Phosphonic Acids 137

4.1 Introduction 137

4.2 Structural Trends and Properties of Functionalized Metal Phosphonates 138

4.2.1 Monophosphonates 138

4.2.1.1 Metal Alkyl- and Aryl-Carboxyphosphonates 138

4.2.1.2 Hydroxyl-Carboxyphosphonates 143

4.2.1.3 Nitrogen-funcionalized phosphonates 147

4.2.1.4 Metal Phosphonatosulphonates 149

4.2.2 Diphosphonates 150

4.2.2.1 Aryldiphosphonates: 1,4-Phenylenebisphosphonates and Related Materials 151

4.2.2.2 1-Hydroxyethylidinediphosphonates 155

4.2.2.3 R-Amino-N,N-bis(methylphosphonates) and R-N,N′]bis(methylphosphonates) 156

4.2.3 Polyphosphonates 163

4.2.3.1 Functionalized Metal Triphosphonates 163

4.2.3.2 Functionalized Metal Tetraphosphonates 167

4.3 Some Relevant Applications of Multifunctional Metal Phosphonates 174

4.3.1 Gas Adsorption 175

4.3.2 Catalysis and Photocatalysis 175

4.3.3 Proton Conductivity 176

4.4 Concluding Remarks 181

References 181

5 Hybrid Multifunctional Materials Based on Phosphonates, Phosphinates and Auxiliary Ligands 193

5.1 Introduction 193

5.1.1 Phosphonates and Phosphinates as Ligands for CPs: Differences in Their Coordination Capabilities 195

5.1.2 The Role of the Auxiliary Ligands 196

5.1.2.1 N-Donors 196

5.1.2.2 O-Donors 198

5.2 CPs Based on Phosphonates and N-Donor Auxiliary Ligands 199

5.2.1 2,2′-Bipyridine and Related Molecules 199

5.2.2 Terpyridine and Related Molecules 210

5.2.3 4,4′-Bipy and Related Molecules 210

5.2.4 Imidazole and Related Molecules 222

5.2.5 Other Ligands 225

5.3 CPs Based on Phosphonates and O-Donor Auxiliary Ligands 228

5.4 CPs Based on Phosphinates and Auxiliary Ligands 233

5.5 Conclusions and Outlooks 240

References 241

6 Hybrid and Biohybrid Materials Based on Layered Clays 245

6.1 Introduction: Clay Concepts and Intercalation Behaviour of Layered Silicates 245

6.2 Intercalation Processes in 1 : 1 Phyllosilicates 247

6.3 Intercalation in 2 : 1 Charged Phyllosilicates 252

6.3.1 Intercalation of Neutral Organic Molecules in 2: 1 Charged Phyllosilicates 252

6.3.2 Intercalation of Organic Cations in 2 : 1 Charged Phyllosilicates: Organoclays 256

6.4 Intercalation of Polymers in Layered Clays 263

6.4.1 Polymer–Clay Nanocomposites 263

6.4.2 Biopolymer Intercalations: Bionanocomposites 269

6.5 Uses of Clay–Organic Intercalation Compounds: Perspectives towards New Applications as Advanced Materials 275

6.5.1 Selective Adsorption and Separation 276

6.5.2 Catalysis and Supports for Organic Reactions 280

6.5.3 Membranes, Ionic and Electronic Conductors and Sensors 281

6.5.4 Photoactive Materials 284

6.5.5 Biomedical Applications 284

References 286

7 Fine-Tuning the Functionality of Inorganic Surfaces Using Phosphonate Chemistry 299

7.1 Phosphonate-Based Modified Surfaces: A Brief Overview 299

7.2 Biological Applications of Phosphonate-Derivatized Inorganic Surfaces 300

7.2.1 Phosphonate Coatings as Bioactive Surfaces 300

7.2.1.1 Supported Lipid Bilayer 300

7.2.1.2 Surface-Modified Nanoparticles 303

7.2.2 Specific Binding of Biological Species onto Phosphonate Surfaces for the Design of Microarrays, 304

7.2.2.1 Single- and Double-Stranded Oligonucleotides 304

7.2.2.2 Proteins and Other Biomolecules 306

7.2.3 Calcium Phosphate/Bisphosphonate Combination as a Route to Implantable Biomedical Devices 308

7.3 Conclusion 314

References 315

8 Photofunctional Polymer/Layered Silicate Hybrids by Intercalation and Polymerization Chemistry 319

8.1 Introduction 319

8.2 Lighting Is Changing 320

8.3 Generalities 321

8.3.1 Layered Silicates 321

8.3.2 Polymer/Layered Silicate Hybrid Structures 322

8.3.3 Methods of Preparation of PNs 323

8.4 Functional Intercalated Compounds 324

8.4.1 Dyes Intercalated Hybrids and (Co)intercalated PNs 324

8.4.2 Light-Emitting Polymer Hybrids 331

8.4.2.1 Poly( p-Phenylene Vinylene)-Based Polymer Hybrids 331

8.4.2.2 Poly(fluorene)-Based Polymer Hybrids 333

8.5 Conclusions and Perspectives 337

References 338

9 Rigid Phosphonic Acids as Building Blocks for Crystalline Hybrid Materials 341

9.1 Introduction 341

9.2 O verview of the Synthesis of Rigid Functional Aromatic and Heteroaromatic Phosphonic Acids 343

9.3 Synthetic Methods to Produce Phosphonic-Based Hybrids 346

9.4 Hybrid Materials from Rigid Di- and Polyphosphonic Acids 347

9.5 Hybrid Materials from Rigid Hetero-polyfunctional Precursors 357

9.5.1 Phosphonic–Carboxylic Acids 357

9.5.2 Phosphonic–Sulphonic Acids 366

9.5.3 O ther Functional Groups 368

9.6 Hybrid Materials from Phosphonic Acids Linked to a Heterocyclic Compound 369

9.6.1 Aza-heterocyclic 369

9.6.2 Thio-heterocycles 373

9.7 Physical Properties and Applications 376

9.7.1 Magnetism 376

9.7.2 Fluorescence 378

9.7.3 Thermal Stability 382

9.7.4 Drug Release 384

9.8 Conclusion and Perspectives 386

References 387

10 Drug Carriers Based on Zirconium Phosphate Nanoparticles 395

10.1 Introduction 395

10.1.1 Zirconium Phosphates 396

10.1.2 Pre-intercalation and the Exfoliation (Layer-by-Layer) Method 397

10.1.3 Direct Ion Exchange of ZrP 399

10.1.4 Direct Ion Exchange Using θ-ZrP 400

10.2 Drug Nanocarriers Based on θ-ZrP 402

10.2.1 Insulin 402

10.2.2 Anticancer Agents 410

10.2.2.1 Nanoparticles and the Enhanced Permeability and Retention Effect 410

10.2.2.2 Cisplatin 410

10.2.2.3 Doxorubicin 418

10.2.2.4 Metallocenes 422

10.2.3 Neurological Agents 428

10.2.3.1 CBZ 429

10.2.3.2 DA 430

10.3 Conclusion 431

References 431