N4-Macrocyclic Metal Complexes

Contents......Page 5
Preface......Page 15
Contributors......Page 17
1. The Basic Concepts of Energy Metabolism......Page 19
2.1. Heme/Cu Terminal Oxidases (HCOs)......Page 23
2.2. Cytochromes bd......Page 29
3. Biomimetic Catalysis of O[sub(2)] Reduction......Page 30
3.1. Simple Fe Porphyrins......Page 33
3.2. Functional Analogs of the Heme/Cu Site......Page 37
3.3. Possible Physiological Role of Cu[sub(B)] from Biomimetic Electrocatalytic Studies......Page 42
4. Summary and Conclusions: Lessons of Biomimetic O[sub(2)] Reduction for the Design of Fuel Cell Catalysts......Page 50
Acknowledgments......Page 53
References......Page 54
1. Introduction......Page 59
2. Reaction Pathways for the Reduction of Molecular Oxygen......Page 60
3. Interaction of O[sub(2)] with Active Sites and the Redox Mechanism......Page 64
4. Two-Electron Reduction Catalysts for the Reduction of Molecular Oxygen......Page 75
5. Four-Electron Reduction Catalysts......Page 78
6. Conclusions......Page 91
References......Page 93
1. Why Search for a Non-Pt Based Catalyst for the Reduction of O[sub(2)] in PEM Fuel Cells?......Page 101
2.1. The Early Days: 1964–1989......Page 106
2.2. Molecular Structure of the Catalytic Site(s)......Page 109
3.1. Kinetic Aspects of Electrochemical Oxygen Reduction......Page 139
3.2. Mechanistic Aspects of Electrochemical Oxygen Reduction......Page 145
4. Important Factors for the Use of Non-Noble Metal Electrocatalysts in PEM Fuel Cells for Automotive Applications......Page 148
5. Conclusions......Page 155
References......Page 157
1. Introduction......Page 166
2.1. Assimilatory Nitrite Reductases......Page 168
2.2. Dissimilatory Nitrite Reductases......Page 172
2.3. Nitric Oxide Reductases......Page 174
3.1. Nitrite......Page 176
3.2. Nitric Oxide, NO......Page 185
3.4. Co-Denitrification......Page 194
3.5. Nonbiomimetic substrates......Page 195
4. Conclusions......Page 197
References......Page 198
1. Introduction......Page 208
2. Electroreduction of CO[sub(2)] on Metallic Cathodes......Page 210
3. Biphenantroline and Bypiridine Hexaazacyclophane Systems......Page 212
4.1. Studies in Solution for Ni Cyclam Systems and Electrochemical Reduction of CO[sub(2)]......Page 221
4.2. Studies in Supramolecular Systems......Page 232
4.3. Modified Electrodes with [Ni (cyclam)][sup(2+)]......Page 235
5.1. Phthalocyanines Complexes in Solution......Page 237
5.2. Porphyrins Complexes in Solution......Page 238
5.3. Studies in Supramolecular Systems......Page 242
5.4. Studies in Modified Electrodes......Page 244
6. Conclusions......Page 260
References......Page 261
1. Build-up of Supramolecular Porphyrins Based on Metal–Ligand Coordination......Page 272
1.1. Supramolecular Porphyrin Assemblies by Axial Coordination......Page 273
1.2. Supramolecular Assembly Using Peripheral Pyridyl–Substituents......Page 277
2. Synthesis and Characterization of Tetrametallated Pyridyl Porphyrins......Page 282
2.1. Syntheses......Page 284
2.2. Characterization......Page 286
3. Catalytic and Electrocatalytic Properties......Page 295
3.1. Hydrocarbon Oxidation......Page 296
3.2. Tetraelectronic O[sub(2)] Reduction......Page 298
4. Electrochemical and Photoelectrochemical Properties of Porphyrin Films......Page 304
4.1. Electrochemical Properties of M-TRP Films......Page 305
4.2. Photocatalytic Properties......Page 316
5. Final Remarks......Page 318
References......Page 319
1. Introduction......Page 332
2.1. Porphyrin and Salen Complexes......Page 335
2.2. Phthalocyanine complexes......Page 338
3. Thiols......Page 339
3.2. Phthalocyanine Complexes......Page 340
4. Sulfur Dioxide and Sulfur Oxoanions......Page 346
4.1. Porphyrin Complexes......Page 347
4.2. Phthalocyanine complexes......Page 348
5.1. Porphyrin Complexes......Page 349
5.2. Phthalocyanine Complexes......Page 354
6.1. Porphyrin Complexes......Page 356
6.2. Phthalocyanine Complexes......Page 358
8. Hydrazine/hydroxylamine......Page 359
8.1. Porphyrin Complexes......Page 360
8.2. Phthalocyanine Complexes......Page 362
References......Page 364
1. Introduction......Page 379
3.1. Doped Electropolymerized Polypyrrole and Polythiophene Films......Page 381
3.2. Electropolymerization of Pyrrole or Thiophene-Substituted N[sub(4)]-Complexes......Page 385
3.3. Immobilization of Multicharged Porphyrins into Pre-Electropolymerized Polypyrrole Films Bearing Functionnal Groups......Page 396
3.4. Electropolymerization of Amino-, Hydroxy- and Vinyl-Substituted N[sub(4)]-Complexes......Page 400
3.5. Electrodeposited Films of Nickel N[sub(4)]-Complexes in Alkaline Solution......Page 411
3.6. Electropolymerized Films of Salen Complexes......Page 417
3.7. Miscellaneous Electrodeposition Processes......Page 422
4.1. Electroassisted Biomimetic Reduction of Molecular Oxygen: Mechanistic and Electrochemical Approach......Page 424
4.2. Electropolymerized N4-Macrocyclic Films as Electrochemical Sensors for Nitric Oxide in Solution......Page 430
4.3. Miscellaneous Significant Examples......Page 433
5. Conclusions......Page 438
References......Page 439
1. Introduction......Page 455
2.1 Synthesis and Characterization of β-Pyrrole Brominated meso-Tetraphenylporphyrins......Page 458
3. Effect of the Br Substituents and Solvent Interactions on the UV–Visible Spectra......Page 461
4. Electrochemical Behavior of β-Pyrrole Brominated Metalloporphyrins......Page 462
4.1. Electroreduction Behavior of β-Pyrrole Brominated Metalloporphyrins......Page 464
4.2. Electrochemical Oxidation Behavior of β-Pyrrole Brominated Metalloporphyrins......Page 466
4.3. Electrochemical Behavior of Water-Soluble β-Pyrrole Brominated Porphyrins......Page 468
5. Spectroelectrochemical Studies of β-Pyrrole Brominated Metalloporphyrins......Page 469
6. Effect of the Br Substituents on Axial Ligand Binding......Page 472
7. Summary......Page 474
References......Page 476
1. Introduction......Page 483
2. Essentials of Photoelectrochemical Reactions......Page 484
3.1. Preparation of Thin Films......Page 486
3.2. Semiconductor Characteristics of Solid Phthalocyanine Films......Page 487
3.3. Position of Frontier Energy Levels in Phthalocyanines......Page 489
3.4. Photocurrent Direction at Phthalocyanine Electrodes......Page 490
3.5. Role of Higher Excited States......Page 494
3.6. Reactant Adsorption......Page 497
3.7. Surface Defects......Page 498
4.1. Sensitization of Nanoparticulate Semiconductors......Page 510
4.2. Sensitization of Electrodeposited Semiconductor Thin Films......Page 512
5. Technology Outlook......Page 517
References......Page 519
1. Introduction......Page 532
2.1. The Structure of the Neat Liquid/Liquid Boundary......Page 533
2.2. The Potential Distribution Across the Polarisable Liquid/Liquid Interface......Page 535
3.1. Electronic Transitions and Lifetime of Excited States in Porphyrin-Based Compounds......Page 538
3.2. Ultrafast Relaxation in Porphyrin Ion Pairs......Page 541
3.3. Interfacial Photoelectrochemistry vs. Time-Resolved Spectroscopy......Page 544
4. Organisation of Water-Soluble Porphyrins at the Liquid/Liquid Interface......Page 547
4.1. Excess Charge Associated with the Specific Adsorption of Ionic Porphyrins......Page 549
4.3. Interfacial Molecular Orientation and Lateral Porphyrin Interactions......Page 551
5.1. The Origin of the Photocurrent Responses......Page 560
5.2. Photocurrent Responses as a Function of the Galvani Potential Difference......Page 565
5.3. Dynamics of Photocurrent Relaxation......Page 575
6. Concluding Remarks......Page 581
References......Page 582
1. Introduction......Page 590
2. Computational Details......Page 596
3.1. Influence of the Metal Atom......Page 597
3.2. Influence of the N[sub(4)] Functionalisation......Page 600
3.3. Influence of the Environment: Solvent Effects......Page 606
3.4. Influence of the Environment: Effect of the Absorption on the Electrode......Page 608
4. Conclusions......Page 612
References......Page 613
1. Introduction......Page 617
2.1. Absorption of Light......Page 619
2.2. Linking Chromophores: General Considerations......Page 631
2.3. Energy and Electron Transfer in Photosynthesis......Page 632
2.4. Design of Synthetic Systems: The Molecular Electronics Challenge......Page 636
4. Covalent Species......Page 637
4.1. Covalent Dimers......Page 638
4.2. Covalent Multiporphyrin Arrays Combined with Nonporphyrinic Acceptors or Donors......Page 654
5.1. Hydrophobic Interactions......Page 668
5.2. Axial Bond Formation......Page 673
5.3. Exocyclic Coordination Complexes as Linkers......Page 681
5.4. Membranes, Vesicles, and Micelles: Templated Assembling......Page 688
5.5. Noncovalent Multiporphyrin Assembling with Nonporphyrinic Electron Acceptors......Page 693
6. Cofacial Arrangements......Page 698
7. Multiporphyrin Surface Assemblies......Page 710
7.1. Covalent Attachment of Multiporphyrins......Page 711
7.2. Langmuir–Blodgett Multilayers of Mono- and Bisporphyrin Species......Page 713
7.3. Porphyrin Films......Page 719
8. Conclusions......Page 725
References......Page 726
2. Surface Phenomena and Applications of Azamacrocycles......Page 739
3. Surface Vibrational Spectroscopy......Page 740
3.3. Infrared Reflection–Absorption Spectroscopy (IRRAS)......Page 742
3.5. Surfaces......Page 743
4.1. Hexaazacyclophane and Its Cu(II) Complex......Page 745
4.2. Phthalocyanines and Naphthalocyanines and Their Metal Complexes......Page 747
4.4. Vanadyl naphthalocyanine and Vanadyl Porphine Phenyl Substituted......Page 749
4.5. Azabipiridyl and its Ni(II), Cu(II), and Zn(II) Complexes......Page 751
4.6. Bis(phenylhydrazine)-1,10-Phenanthroline and its Co(II), Ni(II), Cu(II), and Zn(II) Complexes......Page 755
4.7. Cyclam and Cyclamdione and Their Cu(II) Complexes......Page 757
4.8. Dinaphthalenic Ni(II) and Cu(II) Azamacrocycle Complexes Methyl and Phenyl Substituted......Page 758
5. Normal Coordinate Calculations......Page 760
5.1. Hexaazacyclophane and Its Cu(II) Complex......Page 761
5.2. Azabipiridyl Cu(II) Complex......Page 763
5.3. Bis(phenylhydrazine)-1,10-Phenanthroline and Its Cu(II) Complex......Page 764
6. Surface-Enhanced Vibrational and RAIRS Studies......Page 766
6.1. Cyclam and Cyclamdione and Their Cu(II) Complexes......Page 767
6.2. Bis(phenylhydrazine)-1,10-phenanthroline and its Cu(II) Complex......Page 768
6.3. Azabipiridyl and Its Co(II), Ni(II), and Cu(II) Complexes......Page 770
6.4. Naphthalocyanines......Page 776
6.5. Phthalocyanines......Page 782
6.6. Porphyrins......Page 784
6.7. Miscellaneous Macrocycles......Page 787
7. Adsorbate–Substrate Interaction Vibrations......Page 794
7.3. Naphthalocyanine Metal Complexes......Page 795
7.5. Molecular Model and Theoretical Data of the Adsorbate-Substrate Interaction......Page 796
7.6. Azabipiridyl Metal Complexes......Page 797
7.7. Naphthalocyanine and Its Cu(II) Complex......Page 799
7.8. Dinaphthalenic Ni(II) and Cu(II) Azamacrocycle Complexes Methyl and Phenyl Substituted......Page 802
8. New Trends......Page 803
References......Page 804
A......Page 815
C......Page 816
F......Page 818
H......Page 819
K......Page 820
M......Page 821
N......Page 822
P......Page 823
R......Page 825
T......Page 826
X......Page 827
Z......Page 828