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 xiPreface xiii1 Zirconium Phosphate Nanoparticles and Their Extraordinary Properties 11.1 Introduction 11.2 Synthesis and Crystal Structure of α-Zirconium Phosphate 21.3 Zirconium Phosphate-Based Dialysis Process 51.4 ZrP Titration Curves 71.5 Applications of Ion-Exchange Processes 111.6 Nuclear Ion Separations 111.7 Major Uses of α-ZrP 121.8 Polymer Nanocomposites 121.9 More Details on α-ZrP: Surface Functionalization 171.10 Janus Particles 181.11 Catalysis 201.12 Catalysts Based on Sulphonated Zirconium Phenylphosphonates 221.13 Proton Conductivity and Fuel Cells 271.14 Gel Synthesis and Fuel Cell Membranes 301.15 Electron Transfer Reactions 321.16 Drug Delivery 341.17 Conclusions 39References 402 Tales from the Unexpected: Chemistry at the Surface and Interlayer Space of Layered Organic–Inorganic Hybrid Materials Based on γ-Zirconium Phosphate 452.1 Introduction 452.2 The Inorganic Scaffold: γ-Zirconium Phosphate (Microwave-Assisted Synthesis) 462.3 Microwave-Assisted Synthesis of γ-ZrP 482.4 Reactions 512.4.1 Intercalation 512.4.2 Microwave-Assisted Intercalation into γ-ZrP 522.4.3 Phosphate/Phosphonate Topotactic Exchange 522.5 Labyrinth Materials: Applications 572.5.1 Recognition Management 572.5.1.1 Chirality at Play 622.5.1.2 Gas and Vapour Storage 692.5.2 Dissymmetry and Luminescence Signalling 712.5.3 Building DSSCs 752.5.4 Molecular Confinement 772.6 Conclusion and Prospects 78References 793 Phosphonates in Matrices 833.1 Introduction: Phosphonic Acids as Versatile Molecules 833.2 Acid–Base Chemistry of Phosphonic Acids 843.3 Interactions between Metal Ions and Phosphonate Ligands 873.4 Phosphonates in ‘All-Organic’ Polymeric Salts 903.5 Phosphonates in Coordination Polymers 963.6 Phosphonate-Grafted Polymers 973.7 Polymers as Hosts for Phosphonates and Metal Phosphonates 1083.8 Applications 1133.8.1 Proton Conductivity 1133.8.2 Metal Ion Absorption 1173.8.3 Controlled Release of Phosphonate Pharmaceuticals 1193.8.4 Corrosion Protection by Metal Phosphonate Coatings 1253.8.5 Gas Storage 1253.8.6 Intercalation 1263.9 Conclusions 127References 1284 Hybrid Materials Based on Multifunctional Phosphonic Acids 1374.1 Introduction 1374.2 Structural Trends and Properties of Functionalized Metal Phosphonates 1384.2.1 Monophosphonates 1384.2.1.1 Metal Alkyl- and Aryl-Carboxyphosphonates 1384.2.1.2 Hydroxyl-Carboxyphosphonates 1434.2.1.3 Nitrogen-funcionalized phosphonates 1474.2.1.4 Metal Phosphonatosulphonates 1494.2.2 Diphosphonates 1504.2.2.1 Aryldiphosphonates: 1,4-Phenylenebisphosphonates and Related Materials 1514.2.2.2 1-Hydroxyethylidinediphosphonates 1554.2.2.3 R-Amino-N,N-bis(methylphosphonates) and R-N,N′]bis(methylphosphonates) 1564.2.3 Polyphosphonates 1634.2.3.1 Functionalized Metal Triphosphonates 1634.2.3.2 Functionalized Metal Tetraphosphonates 1674.3 Some Relevant Applications of Multifunctional Metal Phosphonates 1744.3.1 Gas Adsorption 1754.3.2 Catalysis and Photocatalysis 1754.3.3 Proton Conductivity 1764.4 Concluding Remarks 181References 1815 Hybrid Multifunctional Materials Based on Phosphonates, Phosphinates and Auxiliary Ligands 1935.1 Introduction 1935.1.1 Phosphonates and Phosphinates as Ligands for CPs: Differences in Their Coordination Capabilities 1955.1.2 The Role of the Auxiliary Ligands 1965.1.2.1 N-Donors 1965.1.2.2 O-Donors 1985.2 CPs Based on Phosphonates and N-Donor Auxiliary Ligands 1995.2.1 2,2′-Bipyridine and Related Molecules 1995.2.2 Terpyridine and Related Molecules 2105.2.3 4,4′-Bipy and Related Molecules 2105.2.4 Imidazole and Related Molecules 2225.2.5 Other Ligands 2255.3 CPs Based on Phosphonates and O-Donor Auxiliary Ligands 2285.4 CPs Based on Phosphinates and Auxiliary Ligands 2335.5 Conclusions and Outlooks 240References 2416 Hybrid and Biohybrid Materials Based on Layered Clays 2456.1 Introduction: Clay Concepts and Intercalation Behaviour of Layered Silicates 2456.2 Intercalation Processes in 1 : 1 Phyllosilicates 2476.3 Intercalation in 2 : 1 Charged Phyllosilicates 2526.3.1 Intercalation of Neutral Organic Molecules in 2: 1 Charged Phyllosilicates 2526.3.2 Intercalation of Organic Cations in 2 : 1 Charged Phyllosilicates: Organoclays 2566.4 Intercalation of Polymers in Layered Clays 2636.4.1 Polymer–Clay Nanocomposites 2636.4.2 Biopolymer Intercalations: Bionanocomposites 2696.5 Uses of Clay–Organic Intercalation Compounds: Perspectives towards New Applications as Advanced Materials 2756.5.1 Selective Adsorption and Separation 2766.5.2 Catalysis and Supports for Organic Reactions 2806.5.3 Membranes, Ionic and Electronic Conductors and Sensors 2816.5.4 Photoactive Materials 2846.5.5 Biomedical Applications 284References 2867 Fine-Tuning the Functionality of Inorganic Surfaces Using Phosphonate Chemistry 2997.1 Phosphonate-Based Modified Surfaces: A Brief Overview 2997.2 Biological Applications of Phosphonate-Derivatized Inorganic Surfaces 3007.2.1 Phosphonate Coatings as Bioactive Surfaces 3007.2.1.1 Supported Lipid Bilayer 3007.2.1.2 Surface-Modified Nanoparticles 3037.2.2 Specific Binding of Biological Species onto Phosphonate Surfaces for the Design of Microarrays, 3047.2.2.1 Single- and Double-Stranded Oligonucleotides 3047.2.2.2 Proteins and Other Biomolecules 3067.2.3 Calcium Phosphate/Bisphosphonate Combination as a Route to Implantable Biomedical Devices 3087.3 Conclusion 314References 3158 Photofunctional Polymer/Layered Silicate Hybrids by Intercalation and Polymerization Chemistry 3198.1 Introduction 3198.2 Lighting Is Changing 3208.3 Generalities 3218.3.1 Layered Silicates 3218.3.2 Polymer/Layered Silicate Hybrid Structures 3228.3.3 Methods of Preparation of PNs 3238.4 Functional Intercalated Compounds 3248.4.1 Dyes Intercalated Hybrids and (Co)intercalated PNs 3248.4.2 Light-Emitting Polymer Hybrids 3318.4.2.1 Poly( p-Phenylene Vinylene)-Based Polymer Hybrids 3318.4.2.2 Poly(fluorene)-Based Polymer Hybrids 3338.5 Conclusions and Perspectives 337References 3389 Rigid Phosphonic Acids as Building Blocks for Crystalline Hybrid Materials 3419.1 Introduction 3419.2 O verview of the Synthesis of Rigid Functional Aromatic and Heteroaromatic Phosphonic Acids 3439.3 Synthetic Methods to Produce Phosphonic-Based Hybrids 3469.4 Hybrid Materials from Rigid Di- and Polyphosphonic Acids 3479.5 Hybrid Materials from Rigid Hetero-polyfunctional Precursors 3579.5.1 Phosphonic–Carboxylic Acids 3579.5.2 Phosphonic–Sulphonic Acids 3669.5.3 O ther Functional Groups 3689.6 Hybrid Materials from Phosphonic Acids Linked to a Heterocyclic Compound 3699.6.1 Aza-heterocyclic 3699.6.2 Thio-heterocycles 3739.7 Physical Properties and Applications 3769.7.1 Magnetism 3769.7.2 Fluorescence 3789.7.3 Thermal Stability 3829.7.4 Drug Release 3849.8 Conclusion and Perspectives 386References 38710 Drug Carriers Based on Zirconium Phosphate Nanoparticles 39510.1 Introduction 39510.1.1 Zirconium Phosphates 39610.1.2 Pre-intercalation and the Exfoliation (Layer-by-Layer) Method 39710.1.3 Direct Ion Exchange of ZrP 39910.1.4 Direct Ion Exchange Using θ-ZrP 40010.2 Drug Nanocarriers Based on θ-ZrP 40210.2.1 Insulin 40210.2.2 Anticancer Agents 41010.2.2.1 Nanoparticles and the Enhanced Permeability and Retention Effect 41010.2.2.2 Cisplatin 41010.2.2.3 Doxorubicin 41810.2.2.4 Metallocenes 42210.2.3 Neurological Agents 42810.2.3.1 CBZ 42910.2.3.2 DA 43010.3 Conclusion 431References 431