Macromolecules Containing Metal and Metal-Like Elements, Volume 9

Alaa S. Abd-El-Aziz is the Associate Vice-President (Academic and Research) at theUniversity ofBritish Columbia Okanagan. In 1997, he was named a Fellow of the Chemical Institute of Canada, and has been the recipient of a number of awards including the Manitoba Outstanding Chemist Award, the Erica & Arnold Rogers Award for Excellence in Research and Scholarship, and the Clifford J. Robson Memorial Award for Excellence in Teaching.Charles Carraher is Professor of Chemistry atFloridaAtlanticUniversity and Associate Director of theFloridaCenter for Environmental Studies. Dr. Carraher previously was Dean of the Charles E.Schmidt College of Science at FAU, Chair of the Science Division at theUniversity ofSouth Dakota and Chair of the Department of Chemistry at Wright State University. His research deals with the general topic of polymers as applied to electronics, computers, biomedicine, instrumentation and construction.Charles Pittman came to Mississippi State in 1983 as Professor of Industrial Chemistry and Catalysis. He was appointed Full Professor in 1975 and University Research Professor in 1977. He is also Research Director of the University/Industry Chemical Research Center.Martin Zeldin is Visiting Senior Research Scholar at the University of Richmond in Virginia. He received his Ph.D. in inorganic chemistry in 1968 from Pennsylvania State University.

• Preface xviiSeries Preface xxi1. Supramolecular Structures and Functions with Inorganic Building Blocks 1Katsuhiko Ariga, Ajayan Vinu, Jonathan P. Hill, Pavuluri Srinivasu, Somobrata Acharya, and Qingmin JiI. Introduction 2II. Hybrid Lipid Thin Films 2III. Layer-by-Layer Assemblies 8IV. Structure Transcription 13V. Functional Mesoporous Hybrids 20VI. Future Perspectives 30VII. Acknowledgments 30VIII. References 302. Self-Assembly of Hydrophilic Polyoxometalate Macroanions in Dilute Solutions 35Melissa L. Kistler, Joe Pigga, and Tianbo LiuI. Introduction 36II. Solution Behavior of POM Macroions: Soluble but Still Aggregate 38III. Characterization of the Supramolecular Structures 40IV. Controlling the Blackberry Formation and Blackberry Size by Changing Solvent Quality 41V. Counterion Association around Discrete POM Macroions 45VI. Counterion Condensation around Blackberries 46VII. Identification of the Driving Forces Responsible for the Blackberry Formation 47VIII. Soft Nature of the Blackberries—Effect of Additional Hydrogen Bonding 47IX. Weak Electrolyte Type POMs 48X. Effect of Additional Electrolytes 49XI. Kinetic Process of Blackberry Formation 52XII. Cation Transport over the Anionic Blackberry Membrane 55XIII. Macroions in Solution: An important Linkage among Simple Ions, Polymers, Colloids, and Biosystems 57XIV. Conclusions 58XV. Acknowledgments 58XVI. References 583. Supramolecular Structures and Polyoxometalates 61Samar K. DasI. Introduction 62II. Supramolecular Features of Polyoxometalate-Supported Transition-Metal Complexes 62III. Polyoxometalate Crown Ether Complexes with Supramolecular cations 91IV. Supramolecular Water Clusters Associated with Polyoxometalates 103V. Concluding Remarks 118VI. Acknowledgements 119VII. References 1204. Supramolecular Coordination Networks Employing Sulfonate and Phosphonate Linkers: From Layers to Open Structures 125George K. H. Shimizu, Jared M. Taylor, and Ramanathan VaidhyanathanI. Introduction 126II. The Sulfonate Group as a Ligand 127III. Layered Metal Sulfonates 128IV. Nonlayered Metal Sulfonates 137A. Dynamic and Crystalline Metal Sulfonate Frameworks 147B. Hydrogen Bonded Second Sphere Coordination Networks 155V. Metal phosphonates 167VI. Conclusion 176VII. References 1775. Transition-Metal-Based Linear Chain Compounds 181Moumita Majumdar, and Jitendra K. BeraI. Introduction 182II. Ligand-Supported Metal Chains 183A. Linear Chains of Chromium 183B. Linear Metal Chains of Cobalt 187C. Linear Chains of Copper 197D. Linear Chains of Nickel 200E. Linear Chains of Palladium 211III. Unsupported Metal Chains 221A. Linear Chain Compounds of Rhodium 221B. Linear Chain of Iridium 233C. The Platinum Blues 241IV. Concluding Remarks 246V. References 2476. Boronate-Linked Materials: Ranging from Amorphous Assemblies to Highly Structured Networks 255Brett M. Rambo, R. William Tilford, Laura M. Lanni, Jie Liu, and John J. LavigneI. Introduction and Scope 256II. Supramolecular Boronate Assemblies 257A. ‘‘Traditional’’ Hydrogen Bonded Supramolecular Assemblies 258B. ‘‘Novel’’ Phenyl-Boron-Phenyl Sandwich Supramolecular Assembly 258C. Coordination-Based Macrocyclic Assemblies 261D. Coordination-Based Linear Assemblies 267III. Covalently Linked Boronate Assemblies 270A. Covalently Linked Macrocyclic and Cage Assemblies 271B. Covalently Linked Linear Assemblies 279C. Covalently Linked Network Assemblies 284IV. Summary and Outlook 289V. References 2917. Mixed-Metal Supramolecular Complexes Coupling Polyazine Light Absorbers and Reactive Metal Centers 295Shamindri M. Arachchige, and Karen J. BrewerI. Introduction 299A. Light Absorption 300i. Molecular Photovoltaics 301ii. Ruthenium Charge Transfer Light Absorbers 301iii. Osmium Charge Transfer Light Absorbers 303B. Solar Water Splitting 304C. Metal Complexes as DNA Targeting Agents 306D. Supramolecular Charge Transfer Complexes 306E. Cyclic Voltammetry of Charge Transfer Light Absorbers 308II. Supramolecular Complexes Coupling Ru(II) or Os(II) Polyazine Light Absorbers and Rh(III) Reactive Metal Centers 309A. The Complexes [(bpy)2Ru(BL)RhH2(PPh3)2]3+ 309i. Redox Properties of [(bpy)2Ru(BL)RhH2(PPh3)2]3+ 309ii. Spectroscopic Properties of [(bpy)2Ru(BL)RhH2(PPh3)2]3+ 311iii. Photophysical and Photochemical Properties of [(bpy)2Ru(BL)RhH2(PPh3)2]3+ 311B. Cyanide-Bridged Ru(II)-Rh(III) Complexes 312i. Redox Properties of Cyanide-Bridged Ru(II)-Rh(III) Complexes 312ii. Spectroscopic Properties of Cyanide-Bridged Ru(II)-Rh(III) Complexes 313iii. Photophysical and Photochemical Properties of Cyanide-Bridged Ru(II)-Rh(III) Complexes 313C. Polyazine-Bridged [(bpy)2Ru(dpp)Rh(bPy)25+ 314i. Redox Properties of [(bpy)2Ru(dpp)Rh(bPy)25+ 314ii. Spectroscopic Properties of [(bpy)2Ru(dpp)Rh(bpy)25+ 314iii. Photophysical and Photochemical Properties of [(bpy)2Ru(dpp)Rh(bpy)25+ 315D. Tridentate-Bridged Complexes: [(ttpy)Ru(tpy-(Ph)n-tpy)Rh(ttpy)]5+ (n = 0−2) 315i. Redox Properties of [(ttpy)Ru(tpy-(Ph)n-tpy)Rh(ttpy)]5+ 316ii. Spectroscopic Properties of [(ttpy)Ru(tpy-(Ph)n-tpy)Rh(ttpy)]5+ 317iii. Photophysical and Photochemical Properties of [(ttpy)Ru(tpy-(Ph)n-tpy)Rh(ttpy)]5+ 317E. Ru(II)-Rh(III) Complexes Bridged with a Flexible Spacer: [(Me2phen)2Ru(Mebpy-CH2-CH2-Mebpy)Rh(Me 2bpy)2]5+ 319i. Redox Properties of [(Me2phen)2Ru(Mebpy-CH2-CH2-Mebpy)Rh(Me2bpy)2]5+ 320ii. Spectroscopic Properties of [(Me2phen)2Ru(Mebpy-CH2-CH2-Mebpy)Rh(Me2bpy)2]5+ 320iii. Photochemical and Photophysical Properties of [(Me2phen)2Ru(Mebpy-CH2-CH2-Mebpy)Rh(Me2bpy)2 ]5+ 321F. Dendrimeric Ru(II)/Os(II)-Rh(III) Complexes: [M{(dpp)Rh(ppy)2}3](PF6)5 321i. Redox Properties of [M{(dpp)Rh(ppy)2}3](PF6)5 322ii. Spectroscopic Properties of [M{(dpp) Rh(ppy)2}3](PF6)5 323iii. Photophysical and Photochemical Properties of [M{(dpp)Rh(ppy)2}3](PF6)5 323G. Extended Supramolecular Architectures with Fe(II)/Ru(II)/Rh(III) 324H. Stereochemically Defined Tridentate-Bridged Ru(II)-Rh(III) Complex 324i. Redox Properties of [(tpy)Ru(tppz)RhCl3](PF6)2 325ii. Spectroscopic Properties of [(tpy)Ru(tppz)RhCl3](PF6)2 326iii. Photophysical and Photochemical Properties of [(tpy)Ru(tppz)RhCl3](PF6)2 326I. Photoinitiated Electron Collection 327i. LA-BL-Rh-BL-LA Supramolecular Assemblies 328ii. Redox Properties of LA-BL-Rh-BL-LA 328iii. Spectroscopic Properties of LA-BL-Rh-BL-LA 330iv. Photochemical and Photophysical Properties of LA-BL-Rh-BL-LA 331v. Photoinitiated Electron Collection on a Rhodium Center 332vi. Photochemistry with LA-BL-Rh-BL-LA Architectures 333III. Supramolecular Complexes Coupling Ru(II) or Os(II) Polyazine Light Absorbers to Reactive Pt(II) Metal Centers 338A. Cyanide-Bridged Ru(II)-Pt(II) Complexes: [(bpy)2(CN)Ru(CN)Pt(dien)](ClO4)2 and [(dien)Pt(NC)(bpy)2 Ru(CN)Pt(dien)](ClO4)4 338i. Redox Properties of [(bpy)2(CN)Ru(CN)Pt(dien)](ClO4)2 and [(dien)Pt(NC)(bpy)2Ru(CN)Pt(dien)](ClO4)4 338ii. Spectroscopic Properties of [(bpy)2(CN)Ru(CN)Pt(dien)](ClO4)2 and [(dien)Pt(NC)(bpy)2 Ru(CN)Pt(dien)](ClO4)4 339iii. Photochemical and Photophysical Properties of [(bpy)2(CN)Ru(CN)Pt(dien)](ClO4)2 and [(dien)Pt(NC)(bpy)2Ru(CN)Pt(dien)](ClO4)4 339B. A Ru(II)-Pt(II) Complex as a Chemodosimeter 340C. Ru(II)-Pt(II) Complexes Bridged by Flexible Spacers 341i. Redox Properties of [(bpy)2Ru(Mebpy-CH2-CH2-Mebpy)PtCl2](PF6)2 341ii. Spectroscopic Properties of [(bpy)2Ru(Mebpy-CH2-CH2-Mebpy)PtCl2](PF6)2 341D. A bpm-Bridged Ru(II)-Pt(II) Complex: [(bpy)2Ru(bpm)PtCl2]2+ 342i. Redox Properties of [(bpy)2Ru(bpm)PtCl2]2+ 342ii. Spectroscopic Properties of [(bpy)2Ru(bpm)PtCl2]2+ 343E. Ru(II)-Pt(II) dpp-Bridged Complexes: [(bpy)2Ru(dpp)PtMe2]2+ and [(bpy)2Ru(dpp)PtCl2]2+ 343i. Redox Properties of [(bpy)2Ru(dpp)PtMe2]2+ and [(bpy)2Ru(dpp)PtCl2]2+ 343ii. Spectroscopic Properties of [(bpy)2Ru(dpp)PtMe2]2+ and [(bpy)2Ru(dpp)PtCl2]2+ 344iii. Photophysical and Photochemical Properties of [(bpy)2Ru(dpp)PtMe2]2+ and [(bpy)2Ru(dpp)PtCl2]2+ 344F. Ru(II)-Pt(II) Complexes Bridged by a BL Ligand with Two Inequivalent Sites 345i. Redox Properties of [(bpy)2Ru(AB)PtCl2](PF6)2 and [(bpy)2Ru(BA)PtCl2](PF6)2 345ii. Spectroscopic Properties of [(bpy)2Ru(AB)PtCl2](PF6)2 and [(bpy)2Ru(BA)PtCl2](PF6)2 346iii. Photophysical and Photochemical Properties of [(bpy)2Ru(AB)PtCl2](PF6)2 and [(bpy)2 Ru(BA)PtCl2 ](PF6)2 346G. DNA Binding of the Ru(II)-Pt(II) Complex: [(tpy)Ru(dtdeg)PtCl]Cl3 347H. Ru(II)-Pt(II) Complexes with Amino Linkages: [(bpy)2Ru(BL)PtCl2](PF6)2(BL = bpy(CONH(CH2)3NH2)2 and phenNHCO(COOHbpy)) 347i. Photophysical Properties and DNA Binding Ability of [(bpy)2Ru(BL)PtCl2](PF6)2 348ii. Photophysical Properties and Photocatalytic Activity of [(bpy)2Ru(BL)PtCl2](PF6)2 348I. Systematic Studies of Ru(II)/Os(II)-Pt(II) Complexes with Polyazine Bridging Ligands 349i. Redox Properties [(bpy)2M(BL)PtCl2](PF6)2 349ii. Spectroscopic Properties of [(bpy)2M(BL)PtCl2](PF6)2 351iii. DNA Binding by [(bpy)2M(dpb)PtCl2](PF6)2 353J. Dendrimeric Ru(II)-Pt(II) Complexes Bridged by Polyazine Bridging Ligands 354i. Redox and Spectroscopic Properties of [Ru{(dpq) (PtCl2)}3](PF6)2 354ii. Multifunctional DNA Binding and Photocleavage Agent: [{(bpy)2Ru(dpp)}2Ru(dpp)PtCl2](PF6)6 355IV. Supramolecular Complexes Coupling Ru(II) Polyazine Light Absorbers to Reactive Pd(II) Metal Centers 356A. Ru(II)-Pd(II) Complexes Bridged by dpp and bpm Ligands: [(bpy)2Ru(dpp)PdCl2](PF6)2 and [(bpy)2 Ru(bpm)PdCl2](ClO4)2 356i. Redox Properties of [(bpy)2Ru(dpp)PdCl2](PF6)2 and [(bpy)2 Ru(bpm)PdCl2](ClO4)2 356ii. Spectroscopic Properties of [(bpy)2Ru(dpp)PdCl2](PF6)2 and [(bpy)2Ru(bpm)PdCl2](ClO4)2 356B. Ru(II)-Pd(II) Complexes Bridged by an Extended Polyazine Ligand: [(tBu2bpy)2Ru(tpphz)PdCl2](PF6)2 357i. Spectroscopic Properties of [(tBu2bpy)2Ru(tpphz)PdCl2](PF6)2 358C. Ru(II)-Pd(II) Complexes Bridged by bpm type Ligands: [(bpy)2Ru(BL)PdMeCl]2+ 358D. A Ru(II)-Pd(II) Complex Bridged by a Flexible Polyazine Bridging Ligand: [(bpy)2Ru(DMB)PdCl2]2+ 359i. Redox and Spectroscopic Properties of (bpy)2Ru(DMB)PdCl2]2+ 359ii. Photochemistry of [(bpy)2Ru(DMB)PdCl2]2+ 359V. Conclusions 364VI. Acknowledgments 366VII. References 3668. Supramolecular Hybrid Materials—Integrating Functionality with Sensing 369Ramo´n Martı´nez-Ma´n˜ez, Fe´lix Sanceno´n, Ana Bele´n Descalzo, and Knut RurackI. Introduction 370II. Enhanced Coordination by Preorganization. Surface Chelate Effect and Signaling 371III. Enhanced Signaling by Preorganization 378IV. Assembly-Disassembly 381V. Selectivity by Polarity and Size. Biomimetic Signaling 386VI. Switching, Gating and Signaling 391VII. Conclusions 399VIII. Acknowledgments 400IX. References 4009. Molecular Recognition Process between Nucleobases and Metal-Oxalato Frameworks 407Oscar Castillo, Antonio Luque, Juan P. Garcıá-Tera´n, and Pilar Amo-OchoaI. Introduction 408A. Molecular Recognition 408B. Nucleobases 409C. Oxalate 412II. Metal-Oxalato-Nucleobase Extended Systems 413III. Other metal-nucleobase 1D Extended Systems 427VI. Hybrid Systems Based on Metal-Oxalato and Protonated Nucleobases 433V. Conclusions 443VI. References 44310. Crystal Engineering of Coordination Polymers 451Marius Andruh, and Catalina Ruiz-Pe´rezI. Introduction 452II. Synthetic Approaches 453A. The Node-and-Spacer Paradigm 454i. Bridging ligands 455ii. Oligonuclear Complexes as Nodes 461a. Alkoxo-Bridged Binuclear Copper(II) Complexes as Nodes 463b. Homobinuclear Complexes with Compartmental Ligands as Nodes 468c. Heterobinuclear Complexes as Node 473d. Heterotrimetallic Coordination Polymers 478B. Flexible Ligand Approach: Polycarboxylates as Anionic Linkers. A Case Study—Malonato Complexes 479i. Dicarboxylates 480ii. The Case of Malonate. 482iii. Influence of the synthetic conditions 482iv. The use of co-ligands 489v. Ligand Adaptation 493vi. Perspectives 497C. The Building-Block Approach 497i. Oxalato-Bridged Coordination Ploymers 498ii. Bisoxamidato Complexes as Building Blocks 501iii. Cyano-Bridged Coordination Polymers 501III. Conclusions and Perspectives 505IV. Acknowledgments 506V. References 506Index 513

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