Applications III. Functional Materials, Environmental and Biological Applications

Comprehensive Organometallic Chemistry III.pdf......Page 1
Introduction and Scope......Page 3
Group III nitrides......Page 4
Group III phosphides, arsenides, and antimonides......Page 10
Single-source Organometallic III-V Precursors......Page 15
Group III nitride precursors......Page 16
Group III phosphide, arsenide, and antimonide precursors......Page 22
Conventional and Single-source Approach to II-VI Materials......Page 24
Growth of III-VI semiconductors......Page 27
Single-source Organometallic Precursors for IV-VI Materials......Page 30
Organometallic Precursors for Copper Indium Sulfide......Page 31
References......Page 32
Introduction......Page 37
Material Synthesis: Top-down versus Bottom-up Approaches......Page 39
Metal-Organic Routes to Materials: Opportunities and Limitations......Page 40
Functional Ceramics: Chemical Composition, Function and Form......Page 43
Co-precipitation......Page 45
Sol-Gel Process......Page 46
Micro-emulsion Technique......Page 48
Hydrothermal and Solvothermal Methods......Page 49
Chemical Vapor Deposition......Page 50
Functional (Nano) Ceramics......Page 52
Metal oxides......Page 53
Metal chalcogenides, nitrides, pnictides......Page 55
Nitride and carbide of silicon and boron......Page 58
Oxides......Page 61
Heterometal chalcogenides......Page 64
Ternary non-oxide ceramics......Page 65
Quaternary Ceramics......Page 66
Conclusions and Outlook......Page 67
References......Page 68
Introduction......Page 73
Monometallic compounds......Page 74
Bi- and trimetallic compounds......Page 76
Synthesis through Methods Other than Thermolysis......Page 78
Stabilization by polymers......Page 79
Stabilization by ligands......Page 81
Stabilization by polyoxoanions......Page 83
Stabilization by ionic liquids......Page 86
Stabilization by the reaction medium......Page 87
Stabilization by ligands......Page 89
Metals......Page 92
Metal oxides......Page 94
Quantum dots; metal chalcogenides, phosphides, and arsenides......Page 95
References......Page 98
Organometallic Complexes for Optoelectronic Applications......Page 102
Linear and non-linear polarizations......Page 103
Frequency doubling and sum frequency generation......Page 104
Third-order non-linear polarization of matter and third-order NLO effects......Page 105
Introduction to the design of second-order NLO chromophores......Page 106
Dispersion-enhanced versus static hyperpolarizabilities......Page 107
Techniques for measuring hyperpolarizabilities......Page 108
Second-order NLO properties of metallocene donor-acceptor compounds......Page 109
Third-order NLO properties of metallocene compounds......Page 112
Group 4......Page 113
Group 9......Page 114
Half-sandwich compounds with eta7- or eta6-rings......Page 115
Groups 6 and 7......Page 116
Group 8......Page 117
Miscellaneous compounds with eta2-eta4 ligands......Page 121
Group 8......Page 122
Group 8......Page 123
Group 10......Page 126
Miscellaneous compounds with eta1-hydrocarbon ligands......Page 127
Group 6......Page 128
Group 13......Page 129
Three-coordinate boranes......Page 130
Second-order materials......Page 131
Third-order properties of polysilanes, germanes, and stannanes......Page 132
NLO Conclusions......Page 133
Photophysical properties of organic and metal-organic materials......Page 134
Basic steps in EL......Page 135
Carrier injection......Page 136
Carrier migration and device heterostructure......Page 137
Carrier recombination......Page 139
OLED Efficiency and Chromaticity: Units......Page 140
Emissive Dopants for Increased OLED Efficiency......Page 142
Confining carriers and triplet excitons in phosphor-doped OLEDs......Page 143
Organometallic complexes as phosphorescent emitters in OLEDs......Page 144
Synthesis of cyclometallated Ir and Pt complexes......Page 146
Excited states in cyclometallated complexes......Page 148
Tuning emission energy in cyclometallated complexes......Page 151
Blue luminescent cyclometallated complexes......Page 154
Using ancillary ligands to modify the excited-state properties......Page 156
Monochromatic OLED Fabrication......Page 158
OLEDs utilizing organometallic emitters......Page 159
Light-emitting electrochemical cells......Page 176
White OLEDs......Page 178
References......Page 183
Metallomesogens......Page 196
Preamble......Page 197
Thermotropic Liquid Crystals......Page 198
Calamitic Mesogens......Page 199
The nematic phase......Page 200
The true smectic phases......Page 201
Polymorphism......Page 202
Mesophases of Disk-like Mesogens......Page 203
Polycatenar Liquid Crystals......Page 204
Lyotropic Liquid Crystals......Page 207
Physical Properties of Liquid Crystals......Page 208
Polarized Optical Microscopy......Page 209
Differential Scanning Calorimetry......Page 210
Small-angle X-ray Diffraction......Page 211
Organometallic Liquid Crystals of the Group 6 Elements......Page 213
Complexes of Bipyridines and Phenanthrolines......Page 216
Complexes of Amidines......Page 217
Ortho-metallated Complexes......Page 218
Complexes of Iron Carbonyls......Page 220
Introduction......Page 222
Monosubstituted ferrocenes......Page 223
1,1’-, 1,3-, and 1,2-disubstituted ferrocenes......Page 228
Influence of Fc on thermal and mesomorphic properties......Page 232
1,1’,3-Trisubstituted Fc derivatives......Page 234
Hydrogen-bonded Fc derivatives......Page 235
Ferrocene-containing liquid-crystalline dendrimers......Page 236
Complexes of beta-Diketonates......Page 239
Complexes of Stilbazoles and Related Ligands......Page 241
Organometallic Liquid Crystals of the Group 10 Elements......Page 243
Complexes of isonitrile ligands......Page 244
Acetylide complexes......Page 247
Carbene complexes......Page 248
ortho-Metallated azo complexes......Page 249
ortho-Metallated azoxy complexes......Page 254
ortho-Metallated imine complexes......Page 255
ortho-Palladated azine complexes......Page 269
ortho-Metallated pyrimidine complexes......Page 271
Other ortho-metallated complexes......Page 274
Allyl Complexes of Palladium(ii)......Page 277
Isonitrile metal halide complexes......Page 278
Ionic bis(isonitrile) complexes......Page 281
Mixed isonitrile acetylide complexes......Page 282
Mixed isonitrile phenyl complexes......Page 283
Carbene Complexes......Page 286
Diacetylide Complexes of Mercury(ii)......Page 287
Concluding Comments......Page 288
References......Page 289
Organometallic Macromolecular Materials......Page 295
Organometallic Polymers......Page 296
Structural Types......Page 297
Ceramic precursors......Page 298
Historical Development of Organometallic Polymers......Page 299
Poly(vinylferrocene)......Page 301
Other organic polymers with metallocene-containing side-groups......Page 303
Polyphosphazenes with ferrocene- or ruthenocene-containing side-groups......Page 308
Polysilanes, polysiloxanes, and polycarbosilanes with metallocene side-groups......Page 309
Polymers with pi-coordinated metals......Page 311
Block co-polymers with pendant metal-containing groups......Page 313
Approaches using ROMP......Page 314
Introduction......Page 316
Polymetallocenylenes......Page 317
Other polymetallocenes with short spacers via polycondensation routes......Page 320
Thermal ROP of silicon-bridged [1]ferrocenophanes......Page 323
Thermal ROP of other strained metallocenophanes......Page 324
Living anionic ROP of strained metallocenophanes......Page 326
Transition metal-catalyzed ROP of strained metallocenophanes......Page 327
Polyferrocenylsilanes in solution......Page 329
Polyferrocenylsilanes in the solid state: thermal transition behavior, morphology, and conformational properties......Page 330
Electrochemical and electronic properties......Page 332
Redox-active polyferrocenylsilane gels......Page 334
Thermal stability and conversion to nanostructured magnetic ceramics......Page 335
Charge-tunable and pre-ceramic microspheres......Page 336
Water-soluble polyferrocenylsilanes: layer-by layer assembly applications......Page 337
Properties of other ring-opened polymetallocenes and related materials......Page 338
Synthetic scope......Page 339
Self-assembly in block-selective solvents......Page 340
Self-assembly in the solid state......Page 342
Polyferrocenylphosphine block co-polymers......Page 343
Transition Metal-catalyzed ROMP of Metallocenophanes......Page 344
Atom-abstraction-induced ROP of Chalcogenido-bridged Metallocenophanes......Page 345
Face-to-face Polymetallocenes via Condensation Routes......Page 346
Introduction......Page 347
Organic spacers......Page 348
Organosilicon spacers......Page 352
Siloxane spacers......Page 354
Polymetallocenes with Long Conjugated Spacer Groups......Page 355
pi-Cyclobutadiene ligands......Page 358
pi-Cyclopentadienyl ligands......Page 361
pi-Arene ligands......Page 362
Polymer synthesis......Page 364
Approaches to the preparation of high molecular weight group 10 metal-acetylide polymers......Page 365
Structural and theoretical studies of polymers and model oligomers......Page 371
Solution properties......Page 372
Optical properties......Page 373
Electrical and photoconductive properties......Page 376
Polymers with Skeletal Metallocyclopentadiene Units......Page 377
Other Polymers with M-C sigma-Bonds in the Main Chain......Page 378
Introduction......Page 380
High molecular weight polystannanes......Page 381
Polymers that Contain Main-chain Metal-Metal Bonds that Involve Transition Elements......Page 386
Polymers that Contain Metal Clusters in the Main Chain......Page 388
Introduction......Page 389
Metallodendrimers with Metals at the Surface......Page 390
Metallodendrimers with Metals at Interior Sites......Page 398
References......Page 401
Introduction......Page 412
Magnetic Charge-Transfer Salts Based on Metallocenes......Page 413
Structure of Magnetically Ordered [MCp*2][acceptor]......Page 414
TCNQ-based Magnets......Page 416
Electron Acceptors that Stabilize Magnetic Ordering......Page 418
DCNQ-based Magnets......Page 420
Electron-transfer Salts Based on Metallocenes and Inorganic Polyoxometalates......Page 422
Hybrid Magnets Containing Metallocenes......Page 424
Magnets Formed by Bimetallic M(ii) Cr(iii) Oxalates and Metallocenes......Page 426
Magnets Formed by Bimetallic MiiFeiii Oxalates and Metallocenes......Page 431
Magnets Formed by Bimetallic MiiRuiii Oxalates and Metallocenes......Page 434
Magnets Formed by Trimetallic Oxalates and Metallocenes......Page 435
Other Hybrid Magnetic Materials......Page 436
Polynuclear Magnetic Molecules Based on Metallocenes......Page 437
Conclusions and Perspectives......Page 438
References......Page 439
Anticancer Compounds......Page 443
Selective Estrogen Receptor Modulators (SERMs)......Page 444
Ferricenium and Ferrocene Polymer Compounds......Page 447
Titanocenes and Molybdenocenes......Page 448
Ruthenium and Osmium Arene Compounds......Page 449
Polynuclear Complexes (with Direct Metal-Metal Bonds)......Page 451
Bacterial......Page 454
Viral......Page 455
Parasites......Page 456
Hypertensive, Inflammation, and Vasodilation......Page 458
References......Page 459
Introduction......Page 463
Receptors Based on Ferrocene......Page 464
Pt- and Au-based Receptors......Page 469
Other Cation Receptors......Page 471
Receptors Based on Cobaltocenium......Page 472
Receptors Based on Ferrocene......Page 474
Other Anion Receptors Based on Metallocenes......Page 478
Rhenium(i) Tricarbonyl Chloride-based Receptors......Page 479
Receptors Based on Ferrocene......Page 481
Other Receptors for Neutral Guest Species......Page 485
Ion-Pair Receptors......Page 487
Nanoscale Receptors: Dendrimers, Organized Films, and Functionalized Nanoparticles......Page 488
Dendrimers......Page 489
Thin Polymer Films and Self-assembled Monolayers......Page 491
Functionalized Nanoparticles......Page 493
Conclusion......Page 494
References......Page 495
Surface Organometallic Chemistry......Page 497
Oxide Supports......Page 498
Groups 1 and 2......Page 499
Group 13: boron, aluminum, and gallium......Page 500
Silicon......Page 501
Tin......Page 502
Group 3, Lanthanide and Actinide Complexes......Page 504
Supported perhydrocarbyl group 4 complexes......Page 506
Supported group 4 hydride complexes......Page 510
Catalytic activity of group 4 hydrides......Page 511
Supported alkoxide and amido group 4 complexes......Page 513
Vanadium......Page 515
Tantalum......Page 516
Supported group 5 hydride complexes......Page 519
Tantalum......Page 522
Chromium......Page 523
Supported molybdenum perhydrocarbyl complexes......Page 525
Supported molybdenum alkoxide complexes......Page 527
Supported tungsten hydride complexes......Page 528
Rhenium......Page 529
Iron......Page 531
Cobalt......Page 532
Rhodium......Page 533
Generalities......Page 535
Characteristics of metal particles......Page 538
General interaction pathway: example of the reaction of tetraalkyltin complexes on platinum particles supported onto silica......Page 540
Silicon......Page 541
Tin......Page 542
Group 16 complexes/group VIII metal surfaces: selenium......Page 546
References......Page 547
Crystal Engineering: From Molecules to Molecular Materials......Page 552
Intermolecular Interactions Involving Organometallic Molecules......Page 554
Strategies to Obtain Hydrogen-bonded Networks Involving Ions......Page 556
Hydrogen-Bonded Networks Templated by Organometallic Sandwich Units......Page 557
Hydrogen-Bonded Networks Formed by Organometallic Sandwich Units......Page 560
Coordination Networks Based on Organometallic Spacers......Page 567
Reactions Between Solids for the Preparation of Supramolecular Adducts......Page 573
Organometallic Crystal Polymorphism, Crystal Isomerization, and Phase Transitions......Page 576
Conclusions......Page 579
References......Page 581
Principles of Biosensors......Page 586
Electrochemical Sensors......Page 587
Soluble ferrocenes......Page 588
Screen-printed ferrocene-based sensors......Page 591
Protein conjugates......Page 592
Small-molecule conjugates......Page 594
Composite Materials Using Ferrocenes......Page 595
References......Page 596
Environmental and Biological Aspects of Organometallic Compounds......Page 600
Introduction......Page 601
Environmental Stability of Organometallic Compounds......Page 602
Stability to Water......Page 603
Biological Alkylation......Page 604
Mechanisms of Biomethylation......Page 606
Microbial Demethylation/Dealkylation......Page 607
Sample Preparation......Page 608
GC-based speciation methods......Page 610
HPLC-based speciation methods......Page 614
Detection methods......Page 618
Aspects of QC/QA in Speciation Analysis......Page 619
Toxicity of Organometallic Compounds......Page 622
Mercury Methylation and Demethylation......Page 624
Cycling of Methylmercury Species in the Environment......Page 625
Lead Methylation and Demethylation......Page 626
Introduction......Page 627
The Behavior of OTCs in the Environment......Page 629
Bioaccumulation and biotransformation......Page 630
Sample preparation methods......Page 631
Analytical methods based on other techniques......Page 632
Effects on organisms......Page 633
A Summary of the Literature up to 1993......Page 634
Novel Organoarsenic Compounds: 1993-2005......Page 635
Arsine sulfides (thio-arsenicals)......Page 636
Organoarsenicals in novel sample types......Page 637
Oxo-arsenosugars and other arsine oxides......Page 638
Arsenobetaine......Page 639
Organoantimony......Page 640
Aerobic microbial biomethylation of antimomy......Page 641
Anaerobic microbial biomethylation of antimony......Page 643
Toxicity of Organoantimony Compounds......Page 644
Volatile Methylsiloxanes (VMSs)......Page 645
High Molecular Weight Organosilicons......Page 647
Silicones in Medicine......Page 648
Organoselenium......Page 649
References......Page 651
Introduction......Page 659
Introduction......Page 660
Polystyrene supports......Page 661
Soluble Polymer Supports......Page 662
Dendrimers as Supports......Page 663
Ring-opening Metathesis (ROM) Polymerization-derived Supports......Page 664
Microencapsulation of Metal Complexes......Page 665
Introduction......Page 666
Complexes of palladium......Page 667
Complexes of cobalt......Page 677
Polymer-supported chromium-phosphine complexes......Page 679
Complexes of ruthenium......Page 683
Other Supported Monodentate Phosphines......Page 684
Polymer-supported Polydentate Phosphines and Their Metal Complexes......Page 686
Achiral Phosphines Attached to Polymer-supported Peptides......Page 694
Polymer-supported Asymmetric Phosphines and Their Metal Complexes......Page 697
Encapsulation and Other Entrapment Procedures......Page 707
Supported Catalysts for use in Olefin Metathesis......Page 710
Polymer-supported Metallocenes......Page 724
Solid-supported Organometallic Synthesis......Page 734
Polymer-supported NHC Ligands and Immobilized Palladium and Rhodium Complexes......Page 736
Polymer-supported Chromium Isocyanides......Page 739
Polymer-supported Palladacyclic Complexes......Page 740
Concluding Remarks......Page 743
References......Page 744
Overview......Page 750
Fe, Ru, and Os Clusters......Page 751
Co, Rh, and Ir Clusters......Page 755
Heterometallic Clusters......Page 756
Metal Clusters as Models for Metal Surfaces......Page 757
Clusters of group 8 metals......Page 759
Clusters of group 9 metals......Page 760
Heterometallic clusters......Page 762
Metal Clusters as Precursors for Nanoscale Materials......Page 764
Applications in Biomedical Imaging and Pharmaceuticals......Page 765
Non-linear Optical (NLO) Properties of Clusters......Page 766
Luminescent Clusters......Page 768
References......Page 771
Organometallic Inclusion and Intercalation Chemistry......Page 776
Introduction to Organometallic Inclusion Chemistry......Page 777
Introduction to cyclodextrins as supramolecular hosts......Page 778
Adducts with sandwich complexes......Page 779
Adducts with half-sandwich complexes......Page 782
Organometallic complexes bearing alkyl, diene, pi-allyl, or carbonyl ligand......Page 784
Cyclodextrins acting simultaneously as first- and second-sphere ligands......Page 786
Cyclodextrins acting simultaneously as first- and transient second-sphere ligands......Page 787
Cyclodextrins as transient second-sphere ligands......Page 788
Calixarenes as second-sphere ligands......Page 789
Calixarenes acting simultaneously as first- and second-sphere ligands......Page 790
Calixarenes acting simultaneously as first- and transient second-sphere ligands......Page 793
Calixarenes as organometallic hosts for organic molecules......Page 794
Dendrimers as organometallic hosts......Page 795
Dendrimers as hosts for organometallic catalysts......Page 798
Dendrimers as third-sphere ligands of ferrocene......Page 800
Proteins as hosts for bioorganometallic complexes......Page 801
Organometallic complexes in polymer matrix......Page 803
Organometallic Clusters......Page 805
Inorganic Hosts for Organometallic Complexes......Page 806
Carceplexes......Page 808
Glycoluril derivatives......Page 809
Introduction to Organometallic Intercalation Chemistry......Page 810
Host structures......Page 811
Synthesis and structural aspects......Page 812
Host structures......Page 814
Electronic structure......Page 815
Synthesis and structural aspects......Page 816
Intercalation into molybdenum trioxide......Page 818
Host structures......Page 819
Organometallic intercalates of metal phosphates......Page 820
Organometallic intercalates of layered clay minerals......Page 821
Intercalation in beta-ZrNCl......Page 822
Zeolites......Page 823
References......Page 824
Green Organometallic Chemistry......Page 831
Introduction......Page 832
Biphasic hydrogenation......Page 833
Supercritical Fluids......Page 834
Homogeneous hydrogenation......Page 835
Asymmetric hydrogenation......Page 837
Fluorous Media......Page 838
Hydrogenation......Page 840
Palladium-catalyzed cross-coupling reactions......Page 841
Sonochemistry......Page 842
Homogeneous catalysis in microreactors......Page 843
Thermoregulated Catalysis......Page 844
Hydroformylation of Olefins on Supported Catalysts......Page 846
Hydroformylation of Olefins in scCO2......Page 847
Hydroformylation of olefins in fluorous media......Page 848
Overview......Page 849
Metal-mediated Polymerizations of Olefins in Aqueous Media......Page 850
Metal-mediated Polymerizations of Olefins in Ionic Liquids......Page 852
References......Page 853