Comprehensive Coordination Chemistry II - From Biology to Nanotechnology 2 ed. in 10 Vol.Set Volume 07 - From the Molecular to the Nanoscale - Synthesis, Structure, and Properties

McCleverty J.A. (ed.) Comprehensive Coordination Chemistry II - From Biology to Nanotechnology 2 ed. in 10 Vol.Set Volume 07 - From the Molecular to the Nanoscale - Synthesis, Structure, and Properties 2003 [pdf 818sc 813c. 21.86mb] Comprehensive Coordination Chemistry II (CCC II) is the sequel to what has become a classic in the field, Comprehensive Coordination Chemistry, published in 1987. CCC II builds on the first and surveys new developments authoritatively in over 200 newly comissioned chapters, with an emphasis on current trends in biology, materials science and other areas of contemporary scientific interest. Cover Page 1 Introduction to Volume 7 2 COMPREHENSIVE COORDINATION CHEMISTRY II 10 Volumes 11 Info on Volume 7 12 Volume 7 13 7.1 High Nuclearity Clusters: Iso and Heteropolyoxoanions and Relatives 13 Introduction 14 Scope 14 Fundamental Units and Building Blocks 14 Basic Principles in Polyoxometalate Cluster Synthesis 15 Vanadates 16 {V12} Clusters 17 {V14} and {V15} Clusters 20 {V18}, { V22}, {V34} Clusters-Clusters Shaped by Encapsulated Templates 22 Tungstates 27 Clusters Incorporating Monovacant Lacunary Fragments 30 {XW11}2 30 {XW11}2{Mo3S4}2 30 {XW11}3 31 Clusters Incorporating Different Types of Trivacant Lacunary Fragments 31 {X2W21} 31 {M9P5W27} 33 {XW9}1:{Eu3SbW24} 33 {XW9}2:{X2W21}/{X2W22} 34 {XW9}3 34 {XW9}4 36 {XW9}11 36 Clusters Incorporating Hexavacant Lacunary Fragments 36 {P8W48} 36 {P5W30} 36 Molybdates 38 From Keggin Ions to {Mo37} Clusters 39 From {Mo36} to {Mo57} Clusters-Two and Three Fragment Clusters Based on {Mo17} Units 39 {Mo154} Big Wheel Clusters 40 Construction of {Mo154}-type clusters 41 Determination of the molecular formula of {Mo154}-type clusters 42 Reactions of the {Mo154}-type Wheels 42 Formation of structural defects 42 Linking of wheels to chains and layers 44 Formation of host guest systems 44 Structural modifications of the big wheel clusters 48 {Mo176} Wheel and Derivatives 49 Comparison between the {Mo154} and {Mo176} big wheel clusters 49 Nucleation processes within a cluster cavity-from a {Mo176} to a {Mo248} cluster 50 Surface ligand exchange on the big wheel clusters 51 Synthesis of Wheels with Electrophiles 52 Synthesis of the big wheel-type clusters with PrIII salts 52 Synthesis of the big wheel clusters with EuIII salts 52 {Mo132} Big Ball Keplerate Clusters 54 Building block scheme for the Keplerate clusters 55 Construction of spherical species with icosahedral symmetry 56 Changing the bridging ligands in the Keplerate clusters 56 Structural derivatives: removing the lid of the Keplerate 57 From {Mo132} to {Mo72M30} spherical clusters (M=Fe, Mo) 57 Formation of molecular barrels {Mo75V20} 58 Formation of solid-state structures with {Mo72Fe30} 59 Molecular hostages and networks of molecular hostages 60 {Mo368} Clusters: a Hybrid Between Wheel- and Ball-shaped clusters 61 Building Block Principles 63 Outlook 64 Acknowledgments 65 References 65 7.2 High Nuclearity Clusters: Metal-Chalcogenide Polynuclear Complexes 69 Introduction 70 Synthetic Approaches to Metal Chalcogen Clusters 70 Molecular Approaches 70 Association of metal cations and chalcogenide or chalcogenolate anions(I) 70 Reduction of a chalcogen by M(ER)n (II) 71 Phosphine chalcogenides as a source of E (III) 71 Insertion of chalcogen into M&z.sbnd;R bonds (IV) 72 Silylated chalcogenide and chalcogenolate reagents (V) 73 Nucleophilic metal chalcogenide complexes (VI) 74 Cluster expansion/condensation by abstraction or induced elimination of a ligand (VII) 75 Excision of a molecular fragment from an extended solid (VIII) 75 Additional methods (IX) 75 Solid-State and Solvothermal Approaches (X) 76 Structure and Bonding 77 Chalcogen-containing Ligands 77 Chalcogenide ligands 77 Organochalcogenolate ligands 78 Di- and polychalcogenide ligands 78 Photophysics of Metal Chalcogen Clusters: Structure-Property Relationships 79 Octahedral rhenium chalcogenide clusters 79 Group 11 metal-chalcogenolate clusters 80 Group 11 metal-chalcogenide clusters 81 Group 12 metal-chalcogenolate clusters 82 Common Structural Types in Metal Cluster Chemistry 83 Cubane-like Clusters 83 Clusters with Octahedral M6E8 Cores 84 Iron-Chalcogen Clusters Based on Fe2E2 Rhombs 86 Cubic Clusters 90 Clusters with Structures Based on Adamantane or Barrelene Cages and Related Fragments 90 Diverse Structures from Widely Applicable Synthetic Routes 93 Clusters from Silylated Chalcogen Reagents 93 Early transition metal-chalcogenide clusters 95 Middle transition metal-chalcogenide clusters 96 Late transition metal-chalcogenide clusters 96 Group 10 metal clusters 96 Group 11 metal clusters 98 Group 12 metal clusters 106 Clusters from E=PR3 107 Cluster Synthesis via Reactive Chalcogenometallates and Related Reagents 109 Clusters synthesized from tetrachalcogenometallate anions [ME4]n- 109 Ternary M/coinage clusters 109 Ternary M/Fe clusters 114 Related main group ligands 114 Clusters from polynuclear metalloligands 116 Clusters Synthesized from Polychalcogenide Reagents 116 Chalcogen-bridged Clusters of the f-block Elements 118 Nanoclusters 121 Copper Selenide and Silver Selenide "Megaclusters" 121 Quantum Confinement Effects 123 The Photophysical Properties of II-VI Nanoclusters 124 References 126 7.3 High Nuclearity Clusters: Clusters and Aggregates with Paramagnetic Centers: Oxygen and Nitrogen Bridged Systems 136 Introduction 136 Explanation and Apology 136 Strategies for Making Polynuclear Cages 137 Serendipitous Assembly 137 Harris Notation 138 Survey of the 3d Metals 138 Vanadium 139 Alkoxides 139 Phosphonates and arsonates 141 Other ligands 142 Chromium 143 Manganese 145 Iron 156 Cobalt 162 Nickel 167 Copper 171 Families of Cages 177 Wheels and Metallocrowns 177 Cubanes 179 Trigonal Prisms 179 Planar Cages Based on Cadmium Iodide Cores 179 Conclusion 180 References 182 7.4 High Nuclearity Clusters: Clusters and Aggregates with Paramagnetic Centers: Cyano and Oxalato bridged Systems 187 Introduction to Molecular Magnetism 188 Transition Metal Cyanide Chemistry 189 Magnetic Materials from Cyanometalate Building Blocks 190 Prussian Blue 190 Prussian Blue Analogues 191 Photomagnetism 192 One-, Two-, and Three-dimensional Compounds from [M(CN)6]n- Precursors 194 One-dimensional compounds 194 Two-dimensional compounds 195 Three-dimensional compounds 199 Single-molecule Magnets 203 Heptacyanometalate Building Blocks 207 Octacyanometalate Building Blocks 211 High-spin clusters 211 One-dimensional compounds 215 Two-dimensional compounds 219 Three-dimensional networks 220 Other Cyanometalate Precursors Containing Paramagnetic Centers 223 Tetracyanometalates 223 Dicyanometalates 223 Oxalate-Based Two- and Three-Dimensional Magnets 224 Basic Principles of Specific Two- and Three-dimensional Network Configurations 224 Structural Studies on Two-dimensional Compounds 227 Magnetic Studies on Two-dimensional Compounds 228 Structural Studies on Three-dimensional Compounds 229 Magnetic Studies on Three-dimensional Compounds 232 Enantioselective Synthesis of Oxalate-Based Magnets 232 Spin Crossover Phenomenon 233 Utilizing the Spin Crossover Phenomenon: From Rational Design to Functional Molecular Materials 233 Structural Changes in Oxalate-based Spin Crossover Systems 234 One-Dimensional Oxalate-Based Magnets 235 Magnetic Compounds Containing Both Oxalate and Cyanide Bridging Ligands 235 Working Towards the Design of Dual Action Materials 235 References 236 7.5 Coordination Polymers: Infinite Systems 240 Structure 240 Modules as Building Blocks 241 Transition metal ions as connectors 241 Lanthanide ions as connectors 241 Metal clusters and polynuclear complexes as connectors 242 Mononuclear metal complexes as connectors 243 Inorganic ligands as linkers 245 Organic ligands as linkers 246 Metalloligands as linkers 248 Counteranions as linkers 251 Solvent molecules as templates 252 Motifs for Infinite Structures 253 One-dimensional structures 253 Two-dimensional structures 253 Three-dimensional structures 253 Interpenetration 254 Functions 254 Porous Function 254 Toward Coordination Polymer Magnets 259 Spin Cross-over Coordination Polymers 262 Chromism 262 Nonlinear Optical Properties 263 Redox Properties 263 Conductivity 264 New Synthesis-Bottom-up Preparation 264 Self-assembling 264 Usual Diffusion Method 264 Hydro(solvo)thermal Method 265 Microwave and Ultrasonic Methods 265 References 265 7.6 Coordination Polymers: Discrete Systems 271 Introduction and Scope 271 Metallostars and Metallodendrimers 272 Metallostars or Metallodendrimers 272 Structural and Synthetic Considerations 273 Sites of Metal Incorporation 273 Synthetic Strategies 274 Metallostars 275 Metallostars Based Upon bpy and phen Domains 275 Metallostars Based Upon tpy Domains 287 Metallostars Based Upon Other Domains 290 Metallodendrimers 292 Metallodendrimers Based Upon bpy and phen Domains 292 Metallodendrimers Based Upon tpy Domains 296 Metallodendrimers and Metallostars Based Upon Other Domains 297 Surface Decoration 299 Metal Cores Decorated with Dendritic Wedges 301 References 305 7.7 Supramolecular Systems: Templating 311 Introduction 311 [2]Catenanes 312 Templated Syntheses of [2]Catenanes 312 1H NMR and Mass Spectrometries of Metal-free Catenane (1) and Copper [2]Catenane Cu(1)+ 314 X-ray Structures of [2]Catenanes 315 [3]Catenanes and Molecular Necklaces 318 The Eight-reacting-centers Approach 319 The Four-reacting-centers Approach 320 Molecular Necklaces 322 [2]Catenanes Obtained by Ring-Closing Metathesis (RCM) 322 Synthesis of Interlocking Rings Using Two Different Transition Metals as Templating and Connecting Centers: Rucu(20.4)3+, Ruz 326 Template Synthesis of a 5-Coordinate Zinc(II) Catenane, The Corresponding Catenand, and Related Copper(II) and Iron(II) Compl 327 [2]Catenane Constructed Around a Ru(Diimine)32+ Derivative Used as a Template 330 Conclusion 330 References 333 7.8 Supramolecular Systems: Self-assembly 335 Introduction 335 Metal-Ligand Self-Assembly 336 Coordination Assemblies 337 Assemblies with Two- and Three-coordinate Metal Ions 338 Assemblies with Four-coordinate Square-Planar Metal Ions 340 Assemblies with Four-coordinate Tetrahedral Metal Ions 346 Assemblies with Five-coordinate Metal Ions 348 Assemblies with Six-coordinate Octahedral Metal Ions 349 Assemblies with Higher Coordination Number (6) Metal Ions 354 Assemblies with Eight-coordinate Dimetal Ions 356 Properties of Coordination Supramolecular Assemblies 356 Function of Coordination Supramolecular Assemblies 358 Outlook 359 References 359 7.9 Metallomesogens 364 Preamble 366 General Introduction 366 Thermotropic Liquid Crystals 367 Calamitic Mesogens 367 Mesophases of Calamitic Mesogens 368 The nematic phase 369 The chiral nematic phase 370 The true smectic phases 370 The crystal smectic phases 371 Polymorphism 372 Discotic Mesogens 372 Mesophases of Disk-like Mesogens 373 Lyotropic Liquid Crystals 373 Physical Properties Of Liquid Crystals 376 Mesophase Characterization 376 Polarized Optical Microscopy 377 Differential Scanning Calorimetry (DSC) 378 Small-angle X-ray Diffraction 379 Macrocyclic Mesogens Forming Columnar Phases 381 Phthalocyanines 381 Peripherally octasubstituted phthalocyanines 382 Phthalocyanines with extended cores 390 Bis(phthalocyaninato)lanthanide complexes 393 Radially substituted phthalocyanines 396 2,3-Naphthalocyanines 401 Tetrapyrazinoporphyrazines 401 Porphyrins 404 -Octasubstituted metalloporphyrins 404 Meso-tetrasubstituted metalloporphyrins 407 Lanthanide complexes of porphyrins 411 Tetrabenzoporphyrins 412 Tetraazaporphyrins 414 Triazolehemiporphyrazine and Triazolephthalocyanine Complexes 416 Tetraaza[14]annulenes 417 Tetraaza[14]cyclohexadecanes 418 Metallacrown Complexes 419 Macroheterocyclic Tetrametallo-organyls 421 Paracyclophanes 424 Metal Complexes of Azacrowns 425 Calix[4]arenes 427 Discotic and Pseudo-Discotic Compounds showing Columnar Mesophases 428 Beta-Diketonate Metal Complexes 428 Bis[1-(substituted-phenyl)-3-alkyl--diketonato]metal complexes with two and four peripheral chains 429 Bis[1-(substituted-biphenyl)-3-substituted--diketonato]metal complexes with two and four peripheral chains 429 Bis[1,3-(substituted-phenyl)--diketonato]metal complexes 433 Complexes with four peripheral chains 433 Complexes with eight peripheral chains 436 Complexes with ten and twelve peripheral chains 438 Complexes with six peripheral chains 440 Mono-, tris-, and tetrakis-[1,3-substituted-phenyl--diketonato] metal complexes 442 Copper Complexes of Anthraquinones 446 Mixed Phenylpyrimidine-1,3-(Substituted-Phenyl)-b-diketonato)MetalComplexes 446 Triketonato and Tetraketonato Metal Complexes 447 Dithiolene Complexes 452 1,2-Dioxime Complexes 453 Dithiooxamide Complexes 457 Hydrazine Complexes 458 Benzalimines 459 Iminoketones 460 Complexes of Pyrazole-based Ligands 466 Metal Complexes Containing Triphenylene Units 466 Metal Carboxylates 428 Carboxylates of Alkali Metals and Monovalent Metals 428 Alkali-earth and Divalent Metal Carboxylates 471 Transition Metal Alkanoates 473 Tetra(alkanoato)dicopper.2 mesogens 473 Other tetraalkanoatedimetal complexes 476 Tetra(benzoato)dimetal complexes 479 Lanthanide carboxylates 482 Complexes of dithiocarboxylates and xanthates 484 Polycatenar Liquid Crystals 484 Introduction 484 Simple Systems 487 Systems Based on Poly(alkoxy)stilbazole Ligands 489 Complexes of group 10 metals 489 Complexes of silver.1 493 Lyotropic mesomorphism of polycatenar complexes of silver.1 495 Systems Based on Other Types of Poly(alkoxy)substituted Ligands 496 Polycatenar Organometallic Complexes 497 Polycatenar Porphyrins 499 Salen Complexes 501 Other Polycatenar Metallomesogens 503 Wedge-shaped Complexes 507 Metallodendrimers 509 Tetrahedral Complexes Of Cui And Metallohelicates 513 Miscellaneous 513 Calamitic Materials 515 Introduction 515 Ionic Metallomesogens 516 Alkylammonium derivatives 516 Complexes of long-chain amines 517 Pyridinium and imidazolium salts 518 Thiolates 520 Dialkylphosphate salts 521 Complexes of Monodentate Ligands 521 Complexes of organophenylenes 521 Complexes of organonitriles 522 Complexes of organoisonitriles 522 Palladium and platinum 522 Gold and silver 523 Mixed isonitrile–acetylide complexes 524 Halogold(I) isocyanide complexes 525 Mixed phenylene–isonitrile gold complexes 527 Acetylide complexes 529 Carbene complexes 530 Complexes of substituted pyridines 532 Ruthenium complexes 532 Rhodium and iridium complexes 532 Gold complexes 534 Palladium and platinum complexes 534 Silver complexes 535 Pyrazole complexes 538 Physical Properties of Complexes of Monodentate Ligands 539 Mesomorphic Coordination Complexes of Bidentate Ligands 540 Dithiolene complexes 540 Dithiobenzoate complexes 540 Nickel and palladium dithiobenzoates 541 Zinc dithiobenzoates 542 Dithiocarbamate complexes 542 Physical properties of mesogens with bidentate sulfur ligands 543 Benzoato complexes 544 Tropolone complexes 544 Complexes ialpha-substituted- beta-dialdehydes and alpha-substituted- beta-diketones 544 Salicylaldehyde derivatives 545 Complexes of bipyridine ligands 546 Complexes of diazabutadiene ligands 548 Complexes with N,O donor sets 548 N,N`-Disalicylidenealkylenediamine complexes 566 Bis(enaminoketonato) complexes 567 Other complexes with N,O donor sets 569 Complexes with N,N` donor sets 571 Ortho-metallated complexes 572 Ortho-metallated azo complexes 572 Ortho-metallated azoxy complexes 577 Ortho-metallated imine complexes 578 Ortho-palladated azine complexes 586 Ortho-metallated pyrimidine complexes 587 Other ortho-metallated complexes 588 Oxo-bridged complexes 590 O-bridged salicylaldimato complexes 590 O-bridged enaminoketonato complexes 590 Organometallic Complexes 591 Tricarbonyliron(0) derivatives 591 eta6-Benzene complexes 592 Ferrocene-containing thermotropic liquid crystals 592 Introduction 592 Monosubstituted ferrocenes 592 Disubstituted liquid-crystalline ferrocenes 594 Trisubstituted ferrocenes 595 Ferrocenophanes 596 Influence of the ferrocene unit on thermal and mesomorphic properties 597 Optically active systems 598 Ferrocene-containing dendrimers 600 Conclusions 601 Metalloporphyrins 601 Crown-ether Complexes 601 Lyotropic Metallomesogens 605 Polymeric Systems 605 Amphiphilic Systems 607 Simple salts 607 Amphiphilic metal complexes 607 Schiff-base complexes 610 Concluding remarks 610 Columnar Systems 611 Conclusions And Acknowledgments 613 References 614 7.10 Sol-Gel Processing of Metal Compounds 635 Introduction 635 Sol-Gel Processing of Metal Salts 636 Hydrolysis 637 Condensation 638 Polycations and polyanions 640 Precipitation vs. Gelation 640 Influence of the Counteranion 641 Sol-Gel Processing of Metal Alkoxides 642 Synthesis of Metal Alkoxides 642 Synthesis from metals and alcohols 642 Synthesis from metal chlorides and alcohols or alcoholates 643 Alkoxo group interchange 644 Exchange of amido groups with alkoxo groups 644 Formation of heterometallic alkoxides 644 Structures of Metal Alkoxides in Solution and the Solid State 645 Sol-Gel Processing of Metal Alkoxides 647 Metal oxo-alkoxides 649 Nonhydrolytic sol-gel processing 650 Organically Substituted Metal Alkoxides 650 Inorganic-organic hybrid materials 653 References 653 7.11 Molecular Electron Transfer 663 Introduction 664 Overview 664 Matters of Principle and Perspective 666 Molecular Properties that Contribute to the Efficiency of Electron Transfer and their Experimental Determination 667 The free energy of the electron transfer step, DeltaGDA0 667 The solvent reorganizational energy, lambdas 667 The reorganizational energy associated with differences in molecular geometry, lambdaM 667 The pre-exponential nuclear frequency term 668 Electronic contributions 668 Experimental determinations of the contributions to electron transfer rate constants 668 The reaction driving force 668 Self-exchange electron transfer reactions 668 Absorption and emission bandwidths 668 Vibronic fine structure 669 The oscillator strength of electron transfer absorptions 669 Absorption and emission band energies 669 General Logic for Discussion of Thermal and Optical Electron Transfer 669 The Franck-Condon Factor 673 The Electronic Factor 674 Perturbation Theory Corrections for the Alteration of the Free Energy of Reaction Terms as a Consequence of D/A Configurational Mixing 676 Corrections to the Reorganizational Energy Terms that Result from D/A Configurational Mixing 677 The Temperature Dependence of Electron Transfer Rates 678 Special Features of Covalently Linked D/A Complexes 679 Observations in The Limit of Weak Electronic Coupling: Outer-Sphere Electron Transfer 681 The [Fe(CN)6]4-,3- Self-exchange Reaction as a Case Study 682 General Considerations: The Significance of kappael in Outer-sphere Electron Transfer Reactions of Transition Metal Complexes 682 Observations on Cobalt(III)-(II) Systems 683 Franck-Condon Factors 689 The solvent reorganizational free energy contributions (chis) 690 Inner-sphere or molecular reorganizational contributions 690 Gas-phase Solution-phase Comparisons 693 Coupling to Vibrational Modes: Gated Electron Transfer and Vibronic Issues 694 Electron transfer coupled to large-amplitude changes in low-frequency vibrationalmodes, intermediates, and gated electron transfer 695 The response of outer-sphere electron transfer rates to specific vibrational excitation: vibronic coupling 698 Optical-Thermal Comparisons in Outer-sphere Electron Transfer Systems 698 Overview and Summary 698 Covalently Linked Dpi Donors and Acceptors 699 Approaches to Interpreting the Properties of Covalently Linked Donor-Acceptor Complexes 703 Mono-atomic bridging moieties 703 Diatomic bridging moieties 703 Polyatomic bridging ligands 704 Some General Considerations Regarding Linked Donor-Acceptor Complexes when there is no Mixing of the Nuclear and Electronic Coordinates 704 Time Frames for Electron Transfer 705 The Mixing of the Nuclear and Electronic Coordinates in Linked Donor-Acceptor Complexes; Vibronic Coupling 706 Concerted D-B and B-A nuclear motions and the PKS/Piepho vibronic coupling models 709 Classification Schemes for Bridged Complexes 709 Experimental Observations in the Limit of Weak Electronic Coupling; Simple, Aromatic Bridging Ligands 710 Electron Transfer Systems in the Intermediate Regime 711 Experimental Observations in the Limit of Very Strong Electronic Coupling 712 Pyrazine-bridged complexes 713 Polypyridyl ligand-bridged complexes in which coupling appears to be promoted by ligand-to-metal charge transfer (hole transfer systems) 718 Complexes with two-atom bridging moieties 718 Covalently Linked, Sigma Donor-Acceptor Systems 723 Overview and Summary 725 Electron Transfer in Larger-Scale Systems 725 Systems Related to Biological Electron Transport 726 Complexes Containing Multiple Donors and/or Acceptors 727 Heterogeneous Electron Transfer Systems 729 Acknowledgements 729 References 729 7.12 Electron Transfer from the Molecular to the Nanoscale 737 Introduction 738 Scope of Coordination Chemistry in Nanoscale Charge Transfer Systems 738 Scope of Charge Transfer Processes in Nanoscale Systems 740 Scope and Organization of this Chapter 740 Size Effects In Nanoscale Systems For Charge Transfer: Top Down And Bottom Up 741 A Chemist's Perspective: A Molecular Orbital Approach 741 Clusters from Atoms 743 From Macrostructures To Nanostructures 744 Classical Electrostatics for a Spherical Particle 744 Semiclassical Particle in a Sphere 746 Polarization Energy for Semiclassical Particle in a Sphere 746 Adiabatic process 746 Vertical processes 748 Optical Excitation 748 Metal Clusters 750 Semiconductor Clusters 753 Soluble or Dispersed Nanoparticles: Coordination and Colloid Chemistry 755 Framework And Models 755 Energy Scales and Absolute Potentials 756 Relating Rate Constant and Conductance 757 Electronic Coupling Mechanisms in Nanostructures and Distance Dependences 759 Activation Barriers 760 Inner-shell barrier 760 Medium reorganization barrier 761 Conducting spheres in a dielectric medium 761 Dielectric spheres in a dielectric medium 761 A conducting sphere and a dielectric sphere in a dielectric medium 762 Two conducting spheres in different dielectric media 762 One reactant embedded in a dielectric shell 763 Model for a self-assembled monolayer 764 Molecular Electron Transfer in Solution 765 Electron Transfer through Monolayers on Metal Electrodes 765 Electron Transfer through Monolayers on Semiconductor Electrodes 766 Electron Transfer in Metal-Molecule-Metal Systems 767 Experimental Studies Of Nanoscale Systems 769 Distance Dependence in Self-assembled Monolayers 769 Kinetic Dispersity 771 Electron Transfer and Coordination Chemistry in Cluster Synthesis 772 Electron Transfer at MPCs 772 Solutions 772 Films 773 Carrier Hopping between Semiconductor Nanoparticles 774 Organizing Strategies And Media 776 Polymers, Dendrimers 776 Self-assembled Monolayers on Solids 778 Porous Solids 779 Concluding Remarks 780 Acknowledgement 780 References 780 7.13 Magnetism from the Molecular to the Nanoscale 784 Fundamental Aspects 784 Magnetic Coupling 785 Polarized Neutron Diffraction 790 Zero-Dimensional Systems 791 Oligonuclear Systems 791 Mixed-valence Species 792 Valence Tautomeric Species 795 Antiferromagnetic Rings 796 Single-molecule Magnets 799 One-Dimensional Systems 807 Haldane Gap Systems 807 Azide-bridged One-dimensional Systems 808 Metal Radical Chains 810 Metal nitroxide chains 810 Oxalato Derivatives 812 References 814 v. 1. Fundamentals : ligands, complexes, synthesis, purification, and structure v. 2. Fundamentals : physical methods, theoretical analysis, and case studies v. 3. Coordination chemistry of the s, p, and f metals v. 4. Transition metal groups 3-6 v. 5. Transition metal groups 7 and 8 v. 6. Transition metal groups 9-12 v. 7. From the molecular to the nanoscale : synthesis, structure, and properties v. 8. Bio-coordination chemistry v. 9. Applications of coordination chemistry v. 10. Cumulative subject index.