Handbook of Organic-Inorganic Hybrid Materials and

IN SOL-GEL CHEMISTRY Marc Henry 1. Introduction , 2. Sol-Gel Chemistry and Molecular Tectonics of Inorganic Compounds 3 ... Supramolecular Organic Ass...

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Handbook of Organic-Inorganic Hybrid Materials and Nanocomposites Volume 1

Hybrid Materials

Edited by Hari Singh Nalwa Formerly at Hitachi Research Laboratory Hitachi Ltd., Ibaraki, Japan

AMERICAN SCIENTIFIC PUBLISHERS 25650 North Lewis Way Stevenson Ranch, California 91381-1439, USA

Contents List of Contributors Volume Listing About the Editor

Chapter 1.

xjj

• •

MOLECULAR TECTONICS IN SOL-GEL CHEMISTRY Marc Henry

1. Introduction 2. Sol-Gel Chemistry and Molecular Tectonics of Inorganic Compounds 2.1. Aqueous Chemistry of Ti l v Species 2.2. Crystalline Titanium(IV) Oxides 2.3. Titanium Dioxide in Materials Chemistry 3. Titanium(IV) Metallo-Organic Complexes 3.1. Titanium(IV) Alkoxides 3.2. Reaction with Tripodal Ligands 3.3. Crystal Engineering of Hybrid Organic-Inorganic Networks 3.4. Coordination Chemistry of Ti , v with O, N Donors 4. Hybrid Organic-Inorganic TiO,-Based Materials 4.1. Hybrid Materials with Si^O—Ti Bonds 4.2. Hybrid Materials Based on Carboxylatc Derivatives 4.3. Hybrid Materials with Si—O—P Bonds 4.4. Hybrid Materials Obtained in the Presence of Organic Templates 4.5. Hybrid Materials Involving Biological Matter 5. Conclusion and Perspectives Refercnces

Chapter 2.

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, 3 3 11 26 31 32 33 37 43 53 63 65 67 59 73 74 nc

OPTICAL PROPERTIES OF FUNCTIONALIZED SOL-GEL-DERIVED HYBRID MATERIALS P. Prosposito, M,

Casalboni

1. Introduction 2. Synthesis of Sol-Gel-Based Materials 2.1. Inorganic Materials 2.2. Hybrid Materials 3. General Properties of Hybrid Materials 3.1. Mechanical Properties 3.2. Porosity 3.3. Surfacc Morphology 3.4. Electrical Properties 4. Optical Properties 4.1. Undoped Materials 4.2. Doped Materials 5. Nonlinear Optical Properties 6. Optical Waveguides 6.1. Planar Waveguides 6.2. Photopatternable Materials 6.3. Passive Laterally Confined Waveguides 6.4. Active Waveguides 7. Other Applications 7.1. Optical Data Storage 7.2. Diffraction Grätings 7.3. Integrated Optical Devices 7.4. Coatings 7.5. Sensors and Biosensors

ix

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CONTENTS

X

8

118

Conclusions and Future Perspectives

119

Acknowledgments References

Chapter 3.

BUILDING HYBRID ORGANIC-INORGANIC MATERIALS USING SILSESQUIOXANES Douglas A. Loy Kamyar

Rahimian

1. Introduction 1.1. History of Polysilsesquioxanes 1.2. Formation of Polysilsesquioxanes 2 Hydrolysis and Condensation Cbemistry 2.1. 29Si NMR as a Probe of Hydrolysis and Condensation Chemistnes 2.2. Hydrolysis and Condensation Mechanisms 2.3. Cyclization Versus Polymerization 2.4. Effects of Monomer Concentration 2.5. Catalyst 2.6. Water: Monomer Ratio 2.7. Solvents 2.8. Monomer Substituent Effects 3. Surface Modification with Silsesquioxanes 4. Formation of Gels , . _ . 5. Postgelation Processing 6. POSS as Building Blocks 7. Polysilsesquioxanes as Building Blocks 8. Bridged Polysilsesquioxanes 8.1. Bridged Polysilsesquioxane Monomers 8.2. Sol-Gel Polymerization 8.3. Thermal Stability and Mechanical Properties 8.4. Engineering Porosity 8.5. Pore Templating 8.6. Surfactant Templating Porosity 8.7. Catalysts 8.8. Metal and Organic Adsorbents 8.9. Optics and Electronics 9. Nonaqucous Formation of Polysilsesquioxanes 9.1. RSiCl 3 /RSi(OEt) 3 /Lewis Acid 9.2. RSiCi 3 //-Butanol 9.3. RSi(ÖR) 3 -Formic Acid 9.4. Polyhydridosiloxane Disproportionation 9.5. RSiH 3 Oxidation 10. Co-Polymerization with Other Monomers 11. Trialkoxysilane Functionalized Polymers 12. Summary Acknowledgments References

Chapter 4.

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. 144 ^ _ l

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J^ " " ^ 56 157 |-'' 160 160

SILICA-ORGANIC HYBRID MATERIALS Sebastian

Polarz

1. Introduction 2. Morphologies of Silica-Organic Hybrid Materials 2.1. Generat Aspects of the Templating Concept 2.2. Supramolecular Organic Assemblies as an Ordering Principle for Porous Silica 2.3. Validity of the Templating Concept for Other Network Systems 3. Mechanisms of Templating 3.1. Synthesis Mechanisms of M41S-Related Materials 3.2. Mechanism Involved in the Nanocasting Procedure

165 167 167

177 ^ ^

CONTENTS Modification, Applications of, and "Nanochemistry" in Porous Silica Materials 4.1. Chemical Application: Modification of Porous Silica Materials 4.2. Catalytical Applications of Porous Silica Materials 4.3. Other Applications 5. Hierarchically Ordered Porous Silica Materials '.'.'.'..'.. 5.1. Macroscopic Shapes of Porous Silica 5.2. Film Technology and Porous Silica Materials 5.3. Alignment of Pores 5.4. Other Examples of Hierarchical Ordering 6. Summary and Outlook References

xi

4.

Chapter 5.

2. 3.

4.

5.

6.

Haas

Introduction 1.1. Inorganic Polymers, Polysiloxanes, and Copolymers 1.2. Sol-Gel Processing of Inorganic and Hybrid Materials 1.3. Classification of Hybrid Polymers and Nanocomposites Precursors, Functionalization, and Networks Reactions, Structures, Processing, and Compositions 3.1. Inorganic Network Formation 3.2. Organic Networks, Crosslinking 3.3. Molecular Dispersion and Phase Formation 3.4. Processing of Hybrid Polymers 3.5. Typical Compositions Properties 4.1. Mechanical Properties 4.2. Density and Thermal Properties 4.3. Optica! Properties 4.4. Electric and Dielectric Properties 4.5. Permeation Properties 4.6. Polarity and Surface Energy Applications 5.1. Coatings and Thin Films 5.2. Bulk Materials, Composites, and Particles 5.3. Fibers and Membranes Summary Appendix Abbreviations References

Chapter 6.

189

192 192 195 ^ 197 197 ,gS

CROSSLINKED HETEROPOLYSILOXANES AS INORGANIC-ORGANIC POLYMERS: PRECURSORS, SYNTHESIS, PROPERTIES, AND APPLICATIONS Karl-Heinz

1.

lg^ 185 187

207 208 209 209 209 210 210 i ' ' 213 215 215 216 2if, 216 221 224 224 224 224 225 225 228 229 ,,,, 2in 2^i) 230

ORGANIC-INORGANIC HYBRID MATERIALS FROM SONOGELS

Nicolas de la Rosa-Fox, Luis Esquivias, Manuel Pinero Acronyms Index 1. Introduction to the Sol-Gel Process 2. Sol-Gel Process Steps (Mixing, Gelation, Aging, Drying, and Sintering) 3. Sonogels 3.1. Pure Silica Sonogels 3.2. Organic-Inorganic Hybrid Materials 3.3. Wet Sonogels 3.4. Dry Sonogels (Xerogels and Aerogels)

241 241 244 -747 247 250 255 256

CONTENTS

xii

3.5. New Trends in OHIM from Sono-Ormosil Physical Properties of OIHM 4.1. Mechanical Properties 4.2. Optica) Properties

4.

Acronyms Acknowledgments

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Rcferences

Chapter 7.

ORGANIC-INORGANIC HYBRID FROM IONOMER Yan Gao, Namita Roy

1. 2.

3. 4.

5.

6.

Choadhury

Introduction Generic Classification of Polymer-Inorganic Hybrids 2.1. Generation 1: Polymer-Inorganic Hybrids via Sol-Gel Reaction 2.2. Generation 2: Hybrids by Intercalation 2.3. Generation 3: Organic-Inorganic Hybrids from Oxomctallate Clusters Organic-Inorganic Hybrid from Ionomer Methods of Hybrid Preparation 4.1. Sol-Gel Chemistry 4.2. Intercalation 4.3. Dendrimer 4.4. Others 4 5. Tailoring of Sol Formulation 4.6. Molecular Control of Sol-Gel Chemistry by Complexation Structure-Property Relationship in the Hybrids 5.1. Structure of Ionomer-Inorganic Hybrids 5 2 Morphological Feature of Ionomer-Inorganic Hybrids: X-Ray Diffraction and Small-Angle X-Ray Scattering 5.3. Thermal Properties 5.4. Other Properties Application of Organic-Inorganic Hybrids Abbreviations References

Chapter 8.

271 272 ^ 273

^ 274 2?5 2?6 276 277 277

277 R„ ^ ^

^ 2% 292

MAGNETIC ORGANIC-INORGANIC HYBRID MATERIALS: SYNTHESIS, STRUCTURES, AND PROPERTIES Pierre Rabu, Marc

Drillon 297

1. Introduction " 2. Weak Interaction Between Organic and Inorganic Molecular Subunits in Polyoxometalates—TTF Based Salts 2.1. Introduction 2 2 Magnetism of Polyoxometallate Based Compounds 2.3. Salts Based on the Organometallic Donor Decamethylferrocene 2.4. Concluding Remarks 3. Molecular Materials with Extended Inorganic Subnetwork 3.1. Introduction 3.2. The 2D and 3D Transition Metal Oxalate Based Magnets 3.3. Concluding Remarks • 4. Streng Interaction Througli Covalent Bond Between Organic and Inorganic Subnetwork in Transition Metal Phosphonates 4.1. Introduction 4.2. Synthesis 4.3. Structures and Magnetic Properties 4.4. Concluding Remarks

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CONTENTS 5.

The Insertion Compounds 5.1. Introduction 5.2. Compounds with Weak Guest-Host Interaction: The MPS, Series '.'.'.'.'. 5.3. Strong Guest-Host Interaction in Hydroxide-Based Layered Compounds 5.4. Concluding Remarks References

Chapter 9.

xüi 326 ^2A 327 332 34g 34g

LIGHT EMISSION FROM ORGANIC-INORGANIC HYBRIDS LACKING ACTIVATING CENTERS

L. D. Carlos, R. A. Sä Ferreira, V de Zea Bermudez 1. Introduction 2. Sol-Gel Method 2.1. Main Concepts 2.2. Process Parameters and Structural Evolution 3. Amine-Functionaiized Cross-Linked Hybrids 3.1. Synthesis 3.2. Loeal Structure 3.3. Photoluminescence Spectroscopy: The Chemical-Physical Nature of the White-Light Luminescence 3.4. Color Coordinates 3.5. Absolute Emission Quantum Yields 3.6. Recombination Mechanisms 4. Summary Acknowledgments References

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