Molecules at Work: Selfassembly, Nanomaterials, Molecular Machinery

Preface XIII

List of Contributors XXI

Part I Self Assembly 1

1 Yoctoliter-Sized Vessels as Potential Biological Models 3
Sheshanath V. Bhosale, Bradley E. Wilman, and Steven J. Langford

1.1 Introduction 3

1.2 Cavities on Glass Plates and Gold Surfaces 5

1.3 Preparation and Confirmation of Rigid Yoctowell Cavity 6

1.4 Molecular Sorting 7

1.5 Yoctowell-Based Molecular Recognition Events 9

1.6 Conclusion 11

2 Switchable Host–Guest Interactions of Supramolecular Rings and Cages 13
Guido H. Clever

2.1 Introduction 13

2.2 Host–Guest Chemistry 15

2.3 Switching in Supramolecular Systems 17

2.4 Natural Paragons 19

2.5 Types of External Input and Methods for Analysis 20

2.6 Conclusion 33

Part II NanoMaterials 39

3 Tailored Graphene-Type Molecules by Chemical Synthesis 41
Milan Kivala and Xinliang Feng

3.1 Introduction 41

3.2 Synthetic Concepts toward Expanded PAHs – Nanographenes 43

3.3 Conclusion and Outlook 64

4 Analyzing the Surface Area Properties of Microporous Materials 71
Abbie Trewin

4.1 Introduction 71

4.2 Microporous Materials 74

4.3 Porosity 81

4.4 Porous Materials and Calculating Surface Areas 85

4.5 Summary 92

5 Nanostructured Materials Based on Core-Substituted Naphthalene Diimides 97
Sheshanath V. Bhosale, Bradley E. Wilman, and Steven J. Langford

5.1 Introduction 97

5.2 Synthesis of Novel cNDI Derivatives 99

5.3 Electron Transfer 102

5.4 Supramolecular Self-Assembly of cNDI 105

5.5 Conclusion 110

6 Metal Phosphides: From Chemist’s Oddities to Designed Functional Materials 113
Sophie Carenco, Matthieu Demange, Cedric Boissiere, Clement Sanchez, and Nicolas Mezailles

6.1 Introduction 113

6.2 Bulk Metal Phosphides: A Long History 113

6.3 White Phosphorus for the Low-Temperature Synthesis of Metal Phosphide Nanoparticles 115

7 "Artificial Supermolecule": Progress in the Study of II–V Colloidal Semiconductor Nanocrystals 121
Shiding Miao, Alexander Eychmuller, and Stephen G. Hickey

7.1 Introduction 121

7.2 Optical Properties of II–V Nanocrystals 124

7.3 Synthesis of II–V Nanocrystals 133

7.4 Conclusions and Outlook 143

8 Luminescent Dendrimers 155
Giacomo Bergamini

8.1 Introduction 155

8.2 Intrinsic Photochemical and Photophysical Properties of Organic Dendrimers 156

8.3 Energy Transfer and Energy Upconversion in Multichromophoric Dendrimers 161

8.4 Dendrimers as Ligands for Metal Ions 164

8.5 Self-Assembly 168

8.6 Dendrimers as Photoswitchable Hosts 170

8.7 Conclusion and Perspectives 172

9 Fabrication of Ultramicroporous Silica Membranes for Pervaporation and Gas Separation 177
Vittorio Boffa

9.1 Ultramicroporous Silica Membranes 177

9.2 MxOy –Silica Membrane 185

9.3 Hybrid Organic-Silica Membranes 193

9.4 Perspectives in the Fabrication and Application of Silica Membranes 200

10 New Directions in the Fight against Cancer: From Metal Complexes to Nanostructured Materials 207
Santiago Gomez-Ruiz

10.1 Introduction 207

10.2 Metal Complexes in Cancer Treatment 208

10.3 Nanostructured Materials in Cancer Treatments 221

Part III Molecular Machinery 243

11 Molecular Rotors: Imaging Intracellular Viscosity 245
Marina K. Kuimova

11.1 Introduction 245

11.2 Theoretical Background 246

11.3 Biological Applications of Molecular Rotors 247

11.4 Conclusions and Outlook 258

12 Surface-Functionalized Inorganic Colloidal Nanocrystals in Functional Nanocomposite Materials for Microfabrication 263
Chiara Ingrosso, Marinella Striccoli, Angela Agostiano, and Maria Lucia Curri

12.1 Introduction 263

12.2 Colloidal Nanocrystals: Properties, Synthesis, and Surface Functionalization 264

12.3 NC-Based Nanocomposites for Microfabrication 269

12.4 Conclusions and Future Perspectives 279

13 Fluorescence Sensing of Temperature and Oxygen with Fullerenes 285
Mario N. Berberan-Santos and Carlos Baleizao

13.1 Introduction 285

13.2 Thermally Activated Delayed Fluorescence: Fundamental Aspects 287

13.3 Sensing Applications 292

13.4 Conclusions and Future Perspectives 307

14 Going beyond Glucose Sensing with Boronic Acid Receptors 315
Alexander Schiller

14.1 Introduction 315

14.2 Indicator Displacement Assays for the Detection of Sugars 316

14.3 Glucose Sensing with Boronic Acid Receptors 317

14.4 Solution-Phase Sensor Arrays with Boronic-Acid-Appended Bipyridinium Salts 321

14.5 Carbohydrate-Active Enzyme Assays 327

14.6 Boronic-Acid-Appended Bipyridinium Salts at Work – NOVOSIDES 330

14.7 Conclusions and Perspectives 333

15 Design of Novel Iridium Complexes to Obtain Stable and Efficient Light-Emitting Electrochemical Cells 339
Ruben D. Costa

15.1 Brief History of Electroluminescence and Optoelectronic Devices 339

15.2 Light-Emitting Electrochemical Cells: Motivation and Definition 340

15.3 Ionic Transition-Metal Complexes Based on Ir(III) Metal Core for LECs 343

15.4 Strategies to Design Iridium(III) Complexes for Highly Efficient LECs 346

15.5 Strategies to Design Iridium(III) Complexes for Highly Stable LECs 350

15.6 Outlook and Conclusions 356

16 Photochemically Driven Molecular Devices and Machines 361
Serena Silvi

16.1 Introduction 361

16.2 Switches and Logic Gates 363

16.3 Molecular Machines 369

16.4 Conclusions 380

Acknowledgments 381

References 381

Index 385