Handbook of Porphyrin Science: With Applications to Chemistry, Physics, Materials Science, Engineering, Biology and Medicine, Volumes 6-10

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......Page 2
Volume 6: NMR and EPR Techniques
......Page 5
Contents......Page 7
Preface......Page 15
Contributing Authors......Page 17
Contents of Volumes 1–10......Page 25
29 / NMR and EPR Spectroscopy of Paramagnetic Metalloporphyrins and Heme Proteins F. Ann Walker......Page 31
I. Introduction and Background......Page 37
A. Structures and Electron Configurations of Metalloporphyrins......Page 40
A. Proton Chemical Shifts......Page 49
1. Contact Shifts......Page 50
a. Pseudocontact Shifts of Metalloporphyrin Substituents......Page 53
b. Measurement of Magnetic Susceptibility Anisotropies of Ferriheme Proteins......Page 56
c. Residual Dipolar Couplings of Proteins for Structure Determination......Page 59
3. Temperature Dependence of Contact and Pseudocontact Shifts......Page 61
1. Chemical Exchange Line Broadening and EXSY Cross Peaks......Page 63
b. Nuclear Spin-Lattice Relaxation Times, T1......Page 64
c. Nuclear Spin–Spin Relaxation Times, T2......Page 68
1. The Metal Ion.......Page 69
2. The Porphyrin Ring......Page 70
3. The Effect of Axial Ligand Plane Orientation on the Combined Contact and Pseudocontact Shifts of Low-Spin Ferriheme Proteins and Synthetic Hemins with Hindered Axial Ligand Rotation.......Page 80
4. Mechanisms of Spin Delocalization through Chemical Bonds, and Strategies for Separation of Contact and Pseudocontact Shifts......Page 85
1. Substitution of H by CH3 or Other Substituent......Page 87
2. Deuteration of Specific Groups......Page 88
3. 2D 13C Natural Abundance HMQC Spectra and Specific or Complete 13C Labeling of Protohemin for the Assignment of Heme Resonances in Proteins.......Page 89
4. Saturation Transfer NMR Experiments......Page 92
5. NOE Difference Spectroscopy......Page 93
6. Two-Dimensional NMR Techniques......Page 94
A. Resolution and Assignment......Page 99
B. Analysis of Shifts.......Page 105
1. Curvature in the Curie Plot over the Temperature Range of the Measurement......Page 107
b. Nonzero Intercepts of the Curie Plot......Page 109
2. Empirical Methods......Page 110
1. Iron(I) Porphyrins......Page 113
a. Six-Coordinate Diamagnetic Complexes......Page 114
3. Intermediate-Spin Iron(II) Porphyrins: Observed Shifts and the Mechanism of Spin Delocalization......Page 115
a. Models of Deoxyhemoglobin and Deoxymyoglobin......Page 123
c. Models for the Heme a3-CuB and Heme-Nonheme Fe Centers of Cytochrome Oxidase and NO Reductase......Page 126
e. N-Alkyl (aryl) Porphyrin Complexes......Page 133
g. Verdoheme Analogs: Iron(II) Complexes of Octaethyloxaporphyrin, OEOP......Page 134
h. “N-confused” or “N-inverted” Iron(II) Porphyrins and Related N-modified Macrocycle Complexes......Page 135
5. Possible Iron(II) Porphyrin π-Cation Radicals......Page 136
a. Five-Coordinate, Monomeric Iron(III) Porphyrin Complexes......Page 137
b. Six-Coordinate Monomeric High-Spin Iron(III) Porphyrin Complexes.......Page 142
ii. Iron(III) Octaethyl- and Tetraphenylchlorin......Page 147
iii. Two Iron(III) Octaethylisobacteriochlorin Isomers......Page 151
iv. An Iron(III) Monooxochlorin Complex......Page 152
vi. The Iron(III) Complex of Tetraphenyl-21- Oxaporphyrin......Page 153
vii. The High-Spin Iron(III) Complexes of Mono-meso-octaethyloxaporphyrin and Mono-meso-octaethylazaporphyrin.......Page 154
d. Bridged Dimeric Complexes of High-Spin Iron(III) Porphyrins and Chlorins......Page 155
7. Intermediate-Spin Iron(III) Porphyrins: Observed Shifts and the Mechanism of Spin Delocalization......Page 158
8. Low-Spin Iron(III) Porphyrins......Page 162
a. Griffith’s Three-Orbital Theory and Experimental EPR Data for Low-Spin Iron(III) Porphyrins and Related Macrocycles......Page 164
i. Effect of Porphyrin Substituents on the Pattern of Spin Delocalization......Page 177
(a) Neutral Imidazole Ligands......Page 181
iii. Effect of Imidazole Plane Orientation on the Paramagnetic Shifts of Low-Spin Iron(III) Porphyrins......Page 182
iv. Bis-Ammine, Amino Ester and Phosphine Complexes......Page 189
v. Mixed-Ligand Complexes......Page 190
c. Observed Shifts and the Mechanism of Spin Delocalization for the (dxz,dyz)4(dxy)1 Ground State......Page 191
d. The Mixed Ground State Behavior of Bis-Cyanide Complexes of Low-Spin Ferrihemes: Observed Shifts and the Mechanism of Spin Delocalization......Page 194
e. The Mixed Ground State Behavior of Bis-(pyridine) Complexes of Low-Spin Ferrihemes: Observed Shift Trends and the Mechanism of Spin Delocalization......Page 197
f. The Mixed Ground State Behavior of Bis-(pyridine) Complexes of Low-Spin Iron(III) Complexes of Oxophlorins and Meso-Amino Porphyrins......Page 204
g. Low-Spin FeIII Complexes of Meso–Meso-Linked 5,5′-Bis(10,15,20-Triphenylporphyrin)......Page 208
h. Five-Coordinate Low-Spin Iron(III) Porphyrins and a Porphycene......Page 209
i. Low-Spin Iron(III) Complexes of Reduced Hemes......Page 212
k. Thermodynamics of Axial Ligation of Iron(III) Porphyrins......Page 216
l. Kinetics of Axial Ligand Exchange......Page 217
9. Electron Exchange Between Low-Spin Iron(III) and Low-Spin Iron(II) Porphyrins......Page 218
a. NMR Spectroscopy of the Nitrophorins......Page 220
i. NMR Investigations of the High-Spin Forms of the Nitrophorins from Rhodnius prolixus......Page 226
ii. pH Titration of the High-Spin Nitrophorins from Rhodnius prolixus......Page 234
iii. NMR Investigations of the Low-Spin Forms of the Nitrophorins from Rhodnius prolixus, and Comparison to Other Heme Proteins......Page 237
iv. Heme Ruffling of the Nitrophorins and Comparison to Other Heme Proteins......Page 247
v. Nitrite Reductase Activity of Nitrophorin 7......Page 251
vi. Dimerization of NP4......Page 252
vii. NMR Spectroscopy of Apo-Nitrophorin 2......Page 253
b. NMR Spectroscopy of the Hemin-Containing Heme Oxygenases.......Page 255
i. NMR Study of High- and Low-Spin Mammalian Heme Oxygenases.......Page 257
ii. NMR Studies of Bacterial Heme Oxygenases......Page 260
(a) Heme Propionate-Polypeptide Interactions Dictate Regioselectivity in HOs......Page 261
(b) NMR Studies of Heme Electronic Structure and its Potential Implications to the Mechanism of Heme Oxidation......Page 266
(c) NMR Spectroscopic Studies of Dynamic Reactivity Relationships......Page 273
c. NMR Spectroscopy of Miscellaneous Other Heme Proteins.......Page 279
a. High-Spin Iron(III) Porphyrin π-Cation Radicals......Page 281
b. Spin-Admixed and Intermediate-Spin Iron(III) Porphyrin π-Cation Radicals......Page 283
d. Iron(III) π-Cation Radicals of Oxophlorins......Page 284
e. Iron(III) Corrole π-Radicals......Page 286
12. Iron(IV) Porphyrins......Page 288
b. Five- and Six-Coordinate Ferryl, (Fe=O)2+, Porphyrin Complexes......Page 289
c. Five-Coordinate Iron(IV) Phenyl Porphyrins......Page 290
13. Iron(IV) Porphyrin π-Radicals.......Page 291
B. Ruthenium and Osmium Porphyrins.......Page 296
a. Observed Shifts and the Pseudocontact Interaction......Page 298
b. Oxidation of Cobalt(II) Porphyrins to Produce π-Radical Dimers.......Page 300
c. Low-Spin Cobalt(II) Oxaporphyrins and Porphodimethenes......Page 301
d. High-Spin Cobalt(II) N-Alkylporphyrins and Alkoxy Adducts of Oxaporphyrins......Page 302
3. Alkylcobalt(III) Porphyrins: Agostic Interactions or Paramagnetic Excited States?......Page 303
D. Rhodium Porphyrins......Page 305
E. Manganese Porphyrins......Page 308
2. High-Spin Manganese(III) Porphyrins......Page 309
4. “Manganese(III) Corrole” at Low Temperatures = Manganese(II) Corrole π-Cation Radical at Ambient Temperatures......Page 310
5. Manganese(III) Porphyrin π-Radicals and Their Transformation to Dichloromanganese(IV) Porphyrins......Page 313
F. Nickel Porphyrins......Page 314
G. Lanthanide Porphyrins.......Page 322
1. Copper(II) and Silver(II) Porphyrins.......Page 324
2. Vanadium(IV) Porphyrins.......Page 327
3. Chromium Porphyrins......Page 328
I. Summary of Paramagnetic Shifts and Mechanisms of Spin Delocalization for the Metalloporphyrins......Page 329
V. Acknowledgments......Page 333
VI. References.......Page 334
30 / Heme Acquisition by Hemophores: A Lesson from NMR Paola Turano......Page 369
I. Biological Background.......Page 370
A. Heme-Loaded HasA......Page 372
a. 1H NMR......Page 374
i. 13C NMR.......Page 376
ii. 15N NMR......Page 379
B. The H83A Variant.......Page 380
A. 1H–15N NMR Spectra......Page 383
1. Chemical Shift Perturbation Mapping......Page 386
2. Spectral Profiling......Page 387
B. The Fate of the Heme......Page 388
IV. Interaction with Hemoglobin......Page 389
V. Concluding Remarks......Page 390
VII. References......Page 391
31 / Structure–Function Relationships Among Heme Peroxidases: New Insights from Electronic Absorption, Resonance Raman and Multifrequency Electron Paramagnetic Resonance Spectroscopies Giulietta Smulevich, Alessandro Feis, Barry D. Howes and Anabella Ivancich......Page 397
I. General Introduction......Page 398
B. Multifrequency Electron Paramagnetic Resonance Spectroscopy......Page 400
II. Superfamily of Plant, Fungal, and Bacterial Peroxidases......Page 402
A. Heme Pocket......Page 403
1. Fe(III) Resting State......Page 404
2. Extended Network of H-Bonds......Page 410
3. Vinyl–Protein Interaction......Page 411
4. Imidazolate Character of the Proximal Iron Ligand.......Page 414
B. Heme Pocket in Catalase–Peroxidases......Page 416
1. KatG from Synechocystis......Page 420
2. KatG from Mycobacterium tuberculosis......Page 424
C. Calcium Binding Sites......Page 426
D. Binding Sites for Substrates: Benzohydroxamic and Salicylhydroxamic Acids......Page 430
E. Ligand Binding......Page 433
F. Catalytic Intermediates......Page 440
1. X-Ray Structures of Intermediates......Page 442
2. Resonance Raman Characterization of Intermediates......Page 446
3. Multifrequency EPR Spectroscopy: Identification and Reactivity of Intermediates......Page 452
III. Superfamily of Animal Peroxidases......Page 459
A. Covalent Links and Heme Structure......Page 460
B. X-Ray Structures: An Overall View......Page 461
C. Resonance Raman and Electronic Absorption Spectroscopies......Page 462
1. Resonance Raman and Electronic Absorption Studies.......Page 466
2. Multifrequency EPR Spectroscopy Combined with Stopped-Flow Electronic Absorption Spectrophotometry.......Page 468
V. References.......Page 472
Index to Volume 6
......Page 485
Volume 7: Physiochemical Characterization 
......Page 500
Contents......Page 502
Preface......Page 510
Contributing Authors......Page 512
Contents of Volumes 1–10......Page 520
32 / Electronic and Magnetic Structures of Iron Porphyrin Complexes Mikio Nakamura, Yoshiki Ohgo and Akira Ikezaki......Page 526
I. Introduction......Page 528
A. Orbital Interactions......Page 532
1. 1H NMR Spectroscopy......Page 537
2. 13C NMR Spectroscopy......Page 540
C. EPR Spectroscopy......Page 545
A. General Considerations......Page 547
1. Axial Ligands......Page 551
2. Electronic Effects of Peripheral Substituents......Page 556
a. Ruffled Deformation......Page 564
b. Saddled Deformation......Page 570
4. Solvent Effects......Page 572
1. Bis-Imidazole Complexes that Adopt the (dxz, dyz)4(dxy)1 Ground State.......Page 578
2. A Bis-Tert-Butylisocyanide Complex Adopting the (dxy)2(dxz, dyz)3 Ground State.......Page 579
A. General Considerations......Page 582
a. Magnetochemical Series......Page 583
b. Four-Coordinate Iron(III) Porphyrin Cation.......Page 585
2. Deformation of the Porphyrin Ring......Page 586
i. Five-Coordinate Complexes......Page 587
ii. Six-Coordinate Complexes......Page 591
b. Saddled Deformation......Page 592
i. Five-Coordinate Complexes......Page 593
ii. Six-Coordinate Complexes......Page 594
C. Electronic Ground State in Intermediate-Spin Complexes......Page 595
A. General Considerations......Page 600
1. [Fe(OETPP)L2]+......Page 601
2. [Fe(OMTPP)L2]+ and [Fe(TBTXP)L2]+......Page 605
3. [Fe(MAzP)L2]± and [Fe(OEP)L2]±......Page 607
4. Structural Consequences of Spin Crossover......Page 612
1. Monoaqua Complexes of Saddled Porphyrins.......Page 616
2. Monoazide Complexes......Page 619
D. Spin Crossover in Monoimidazole Complexes......Page 620
1. [Fe(TMP)L]+ and [Fe(TMTMP)L]+......Page 621
2. [Fe(OETPP)L]+......Page 626
A. One-Electron-Oxidized Products......Page 633
a. High-Spin Iron(III) Porphyrin Cation Radicals......Page 634
b. Mixed High-Spin and Intermediate-Spin Iron(III) Porphyrin Cation Radicals......Page 639
c. Low-Spin Iron(III) Porphyrin Cation Radicals......Page 640
i. Iron(III) with the (dxy)2(dxz, dyz)3 Electron Configuration......Page 641
ii. Iron(III) with the (dxz, dyz)4(dxy)1 Electron Configuration......Page 642
a. Iron(IV) Porphyrins with an FeIV=O Bond......Page 649
b. Iron(IV) Porphyrins without an Fe=O Bond......Page 652
B. Two-Electron-Oxidized Products of Iron(III) Porphyrins......Page 654
1. Oxoiron(IV) Porphyrin Cation Radicals.......Page 655
4. Iron(V) Porphyrins.......Page 659
VII. Acknowledgments......Page 661
VIII. References......Page 662
33 / Optically Active Porphyrin Systems Analyzed by Circular Dichroism Nagao Kobayashi......Page 672
A. Phenomenological and Theoretical Basis.......Page 673
B. Porphyrin Chromophores......Page 674
C. Exciton Coupling......Page 675
A. Natural Heme Systems.......Page 678
B. Synthetic Heme Systems......Page 690
1. Chlorophyll a and Bacteriochlorophyll a and Their Derivatives......Page 698
2. Bacteriochlorophyll c, d, e and g......Page 709
3. Light Harvesting Complex 2 (LH2)......Page 710
B. Synthetic Chlorins, Bacteriochlorins and Their Dimeric and Aggregated Systems......Page 716
V. Synthetic Porphyrin Monomer Systems......Page 721
A. Bis-porphyrin Systems Linked to Optically Active Naphthalene Units......Page 730
B. Dimeric Porphyrin Systems Without Optically Active Substituents......Page 733
C. Oligomeric Porphyrin Systems......Page 744
A. Determination of the Helicity of Polyisocyanides.......Page 755
B. Determination of the Absolute Configurations of Natural Products......Page 757
IX. References......Page 765
34 / Photochemical and Photophysical Properties of Metallophthalocyanines Tebello Nyokong and Edith Antunes......Page 772
List of Abbreviations.......Page 774
I. Introduction......Page 775
A. Singlet Oxygen Quantum Yields (Φ.)......Page 793
B. Photodegradation Quantum Yields (ΦP)......Page 798
D. Triplet State Quantum Yields (ΦT) and Lifetimes ( τT)......Page 800
III. Water Soluble Phthalocyanine Complexes......Page 802
A. Aggregation Behavior......Page 803
1. Sulfonated Derivatives......Page 804
3. Quaternized Derivatives......Page 805
B. Fluorescence Spectra and Quantum Yields (ΦF)......Page 806
b. Other MPc(SO3)n Complexes......Page 817
b. MPc Complexes......Page 838
a. MPc(SO3)mix Complexes......Page 840
2. Carboxylated Derivatives.......Page 841
3. Quaternized Derivatives......Page 842
b. Other MPc(SO3)n Complexes......Page 843
a. Porphyrazine Complexes......Page 844
E. Photobleaching Quantum Yields (ΦP)......Page 845
A. Aggregation Behavior in General......Page 846
B. Unmetalated, Group 1 and Group 2 Phthalocyanine Complexes......Page 848
a. Fluorescence Quantum Yields (ΦF)......Page 855
b. Triplet Quantum Yields (ΦT) and Lifetimes ( τT)......Page 857
c. Singlet Oxygen Quantum Yields (Φ.).......Page 858
d. Photodegradation Quantum Yields (ΦP)......Page 859
b. Triplet Quantum Yields and Lifetimes......Page 860
3. HgPc Complexes......Page 861
a. Fluorescence Quantum Yields......Page 862
b. Triplet Quantum Yields and Lifetimes......Page 863
a. X2Si(IV)Pc Complexes......Page 864
b. Other Group 14 and 15 Phthalocyanine Complexes......Page 865
V. Photocatalytic Reactions......Page 866
A. Sulfur-Containing Compounds......Page 867
1. Phthalocyanine Complexes on Supports.......Page 868
2. Phthalocyanine Complexes in Solution......Page 870
C. Alkanes and Alkenes......Page 872
VI. Conclusions......Page 873
VIII. References......Page 874
35 / Structure, Spectroscopy, Photophysics, and Tautomerism of Free-Base Porphycenes and Other Porphyrin Isomers Jacek Waluk......Page 884
I. Introduction......Page 885
A. Symmetry and Planarity......Page 890
B. Influence of Substituents on the Geometry of the Internal Cavity......Page 894
C. Cis–Trans Tautomerism.......Page 898
A. Electronic Absorption Spectra.......Page 905
1. Absorption Spectra of Porphycenes......Page 909
2. Absorption Spectra of Hemiporphycene, Corrphycene, and Isoporphycene Derivatives......Page 915
B. Perimeter Model Applied for the Elucidation of Absorption and Magnetic Circular Dichroism Spectra......Page 917
C. Low-Temperature Spectroscopy of Porphycene......Page 922
IV. Photophysics......Page 924
A. Mechanism of Excited State Deactivation in Alkylated Porphycenes......Page 929
C. Triplet State Studies......Page 932
A. Tautomerism in Porphyrins......Page 934
1. Coherent Double Hydrogen Tunneling in Isolated Molecules......Page 936
a. Ground State Tautomerism in Polycrystalline Porphycene......Page 941
b. Studies Using Polarized Spectroscopy Techniques......Page 942
c. Tautomerization in the Triplet State......Page 948
3. Single Molecule Studies......Page 949
VI. Summary and Outlook......Page 951
VIII. References......Page 953
36 / Recent Applications of Infrared Spectroscopy and Microscopy in Chemistry, Biology and Medicine Petra Hellwig and Frédéric Melin......Page 962
List of Abbreviations......Page 963
I. Introduction......Page 966
A. The Mid-Infrared or Rock Salt Region......Page 967
1. Square Planar M(II) Porphyrins and Analogs: Metal-Sensitive Bands......Page 968
b. Dioxygen......Page 969
c. Carbon Monoxide......Page 971
e. Nitric Oxide......Page 973
3. M(II) and M(III) Porphyrins: Redox- and Spin-State-Sensitive Bands......Page 975
4. Porphyrin π-Cation Radicals......Page 976
B. Recent Developments in the Near-Infrared......Page 977
1. Modes of a Collective Nature......Page 978
2. Metal–Ligand Vibrations......Page 979
D. Using the Effect of Temperature: T-Derivative Spectroscopy......Page 981
1. Pressure Dependence of Infrared Spectral Features......Page 983
2. Assignment of Heme Doming Modes......Page 984
1. Infrared Microscopy and Imaging......Page 985
2. Working with Synchrotron Light......Page 986
A. Motivation......Page 987
1. Thin Layer Electrochemistry......Page 988
2. Surface-Enhanced Infrared Absorption Spectroscopy......Page 989
1. Studies on Porphyrins and Small Hemoproteins......Page 991
a. Identification of Protonation Sites in Cytochrome c Oxidase......Page 993
b. The bc1 Complex from the Respiratory Chain......Page 997
1. Accessible Time Domains......Page 999
a. Ligand Rebinding......Page 1000
b. Ligand Rebinding in Cytochrome c Oxidase......Page 1001
a. The Approach......Page 1004
b. OH Stretching and H-bonding in Water......Page 1005
E. Perfusion-Induced Approaches; Stopped-Flow and Rapid Mixing......Page 1006
IV. Conclusion......Page 1007
V. References......Page 1008
Index to Volume 7
......Page 1018
Volume 8: Open-Chain Oligopyrrole Systems
......Page 1039
Contents......Page 1041
Preface......Page 1047
Contributing Authors......Page 1049
Contents of Volumes 1–10......Page 1057
37 / BODIPY® Dyes and Their Derivatives: Syntheses and Spectroscopic Properties Aurore Loudet and Kevin Burgess......Page 1063
I. Introduction......Page 1065
A. Fundamental Properties......Page 1066
B. Syntheses of the Unsubstituted BODIPY 1......Page 1068
C. Syntheses of Substituted BODIPYs from Pyrroles and Acid Chlorides or Anhydrides......Page 1069
D. From Pyrroles and Aldehydes......Page 1070
F. Synthesis of Symmetrical BODIPY from Pyrrole-2-Carbaldehyde......Page 1074
A. Introduction......Page 1077
B. Fluorescence Control via Photoinduced Electron Transfer......Page 1080
A. From Electrophilic Substitution Reactions......Page 1086
1. Nitration......Page 1087
2. Halogenation......Page 1088
B. From Nucleophilic Attack on Halogenated BODIPYs......Page 1090
C. From Metal Mediated C-H Functionalization......Page 1094
D. From Nucleophilic Attack at the meso-Position......Page 1098
A. From Electrophilic Substitution Reactions......Page 1101
B. From Coupling or Substitution Reactions.......Page 1102
A. Meso Aryl-, Alkenyl- and Alkynyl-Substituted BODIPYs .......Page 1104
B. 3,5-Aryl-Substituted BODIPYs from Aryl-Pyrroles......Page 1110
1. 3,5-Styryl-BODIPY Dyes......Page 1114
2. 1,3,5,6-Tetrastyryl-BODIPY Dyes. .......Page 1121
D. From Palladium-Catalyzed Coupling Reactions at the 3- and 5-Positions......Page 1123
A. Through-Space Energy Transfer Cassettes.......Page 1127
1. Porphyrin-Based Systems as Models of Photosynthesis......Page 1132
2. Polypyridine Complexes Containing Accessory BODIPY Chromophores......Page 1139
3. Relatively Compact Systems as Potential Probes in Biotechnology......Page 1142
A. Poly(aryleneethynylene)s (PAEs) Co-Containing BODIPY (2,6-Positions)......Page 1148
B. BODIPY-Based Organoboron Polymer......Page 1151
A. With Alkyl Groups......Page 1152
B. With Aryl Groups......Page 1153
C. With Alkyne Groups......Page 1154
D. With Alkoxide Groups......Page 1160
E. Boronium and Borenium BODIPY Cations......Page 1162
X. Use of Metals Other Than Boron......Page 1164
A. Restricted Systems......Page 1166
2. Dyes Based on Benz[c,d]indole.......Page 1174
3. Phenanthrene-Fused BODIPY Systems......Page 1176
5. Bis-BODIPYs Systems......Page 1179
A. Tetra-Aryl Systems......Page 1181
1. Restricted Systems......Page 1188
2. Dyes Based on Benz[c,d]indole......Page 1192
C. Cyclized Aza-BODIPY Systems......Page 1193
D. Other Metals......Page 1195
A. GFP-Chromophore Analogs......Page 1196
B. Fused Perylene Tetracarboxylic Diimide and BODIPY Analog......Page 1200
C. Biimidazol-2-yl-BF2 Complexes......Page 1203
D. Pyridine-Based Systems......Page 1204
E. 2-Ketopyrrole Complexes......Page 1205
F. Azobenzene Derivatives......Page 1206
G. Miscellaneous N,N-Bidentate Diphenyl Boron Chelates......Page 1207
H. Boryl-Substituted Thienylthiazoles.......Page 1210
XIV. Conclusion......Page 1212
XV. References......Page 1215
38 / Supramolecular Chemistry of Pyrrole-Based π-Conjugated Acyclic Anion Receptors Hiromitsu Maeda......Page 1227
I. Introduction......Page 1228
II. Guanidinocarbonyl- and Amidopyrrole-Based Anion Receptors......Page 1231
A. Guanidinocarbonylpyrrole-Based Anion Receptors......Page 1232
B. Amidopyrrole-Based Anion Receptors......Page 1237
A. Dipyrrin- and Dipyrromethane-Based Anion Receptors......Page 1243
B. Dipyrrin- and Bipyrrole-Based π-Conjugated Systems......Page 1248
A. Dipyrrolylquinoxalines.......Page 1252
B. Anion-Responsive Aryl-Bridged Bispyrroles......Page 1262
C. Dipyrrolylpyrazoles Derived from Dipyrrolyldiketones......Page 1265
A. Synthesis and Properties of Boron Complexes of Dipyrrolyldiketones......Page 1267
B. Aryl-Substituted Anion Receptors......Page 1273
C. Anion-Responsive Supramolecular Gels Consisting of Acyclic Anion Receptors......Page 1281
D. Solvent-Assisted Organized Structures from Amphiphilic Anion Receptors......Page 1286
E. Modifications around Boron Units of Acyclic Anion Receptors......Page 1287
VI. Summary......Page 1289
VIII. References......Page 1290
39 / The Synthesis and Properties of Dipyrrins Tabitha E. Wood, Md. Imam Uddin and Alison Thompson......Page 1297
List of Abbreviations......Page 1298
1. Introduction......Page 1299
a. Unsymmetric 5-Unsubstituted Dipyrrins......Page 1301
c. Symmetric 5-Substituted Dipyrrins......Page 1302
3. Synthesis of Dipyrrins by Oxidation of Dipyrromethanes......Page 1304
C. Properties and Reactions of Dipyrrins.......Page 1306
A. Syntheses of Dipyrrinato Complexes......Page 1309
1. Complexation Geometries......Page 1310
2. Scope of Metal Ions in Homoleptic Dipyrrinato Complexes......Page 1312
4. Heteroleptic Dipyrrinato Complexes......Page 1313
6. Supramolecular Dipyrrinato Metal Complexes.......Page 1317
a. Discrete Helical Complexes......Page 1318
b. Metal-Organic Frameworks (MOFs)......Page 1321
7. Chemical Manipulations of Dipyrrinato Complexes......Page 1330
8. Stereochemistry of Dipyrrinato Metal Complexes.......Page 1337
B. Properties and Reactions of Dipyrrinato Complexes......Page 1340
1. Fluorescent Dipyrrinato Metal Complexes......Page 1341
2. Electrochemical Studies of Dipyrrinato Complexes......Page 1343
III. Concluding Remarks......Page 1345
IV. References......Page 1346
40 / Coordination Chemistry of Verdohemes and Open-Chain Oligopyrrole Systems Involved in Heme Oxidation and Porphyrin Destruction Alan L. Balch and Faye L. Bowles......Page 1355
I. Introduction......Page 1356
A. Heme Catabolism......Page 1357
A. Verdoheme Formation by Porphyrin Oxidation......Page 1358
III. Open-Chain Tetrapyrroles from Ring Opening of Verdohemes......Page 1363
A. Free Ligand......Page 1369
B. Dimeric Complexes; The Case of {MnIII( µ-OEB)}......Page 1372
C. Monomeric Biliverdin Complexes, MII(OEB•)......Page 1374
D. Dimeric Complexes Revisited; The Curious Case of {Pd2( µ-OEB)}2.......Page 1380
E. Iron Biliverdin Complexes......Page 1383
V. Metal Complexes of Formylbiliverdin and Related Tetrapyrroles......Page 1390
VI. Some Other Interesting Open-Chain Complexes that Do Not Fit the Above Classification......Page 1397
IX. References......Page 1401
41 / Beyond Dipyrrins: Coordination Interactions and Templated Macrocyclizations of Open-Chain Oligopyrroles Martin Bröring......Page 1405
List of Abbreviations......Page 1406
A. Introductory Remarks and Scope of This Chapter......Page 1409
B. Types of Open-Chain Tri- and Tetrapyrrolic Species......Page 1410
A. Tripyrroles: Prodigiosenes and Related Species......Page 1414
B. Tripyrroles: Tripyrrinones, Tripyrrins, and Related Tripyrroles......Page 1415
C. Tripyrroles: Bis(arylimino)isoindolines [H(bai)]......Page 1418
D. Tripyrroles: Bis(oxazolinyl)pyrroles [H(bop)]......Page 1421
E. Tetrapyrroles: Model Ligands Prepared from Natural Biliverdin and Bilirubin......Page 1423
F. Tetrapyrroles: Oxidative Ring-Opening of Tetrapyrrole Macrocycles......Page 1425
G. Tetrapyrroles: Coupling of Dipyrrolic Building Blocks......Page 1427
H. Tetrapyrroles: Coupling Two Pyrrole Units with a Dipyrrole......Page 1433
I. Tetrapyrroles: Stepwise Coupling of Pyrrolic Precursors......Page 1438
A. Interaction of Prodigiosenes with Metal Ions......Page 1439
B. Tripyrrinone and Tripyrrin Metal Chelates......Page 1440
C. Bis(arylimino)isoindoline Complexes......Page 1451
D. Complexes of Bis(oxazolinyl)pyrroles......Page 1466
E. Behavior of Bilirubin and Biliverdin Toward Metal Ions......Page 1468
F. Mononuclear Tetrapyrrole L1M1 Complexes and Associates......Page 1472
G. Dinuclear Tetrapyrrole L2M2 Complexes......Page 1490
H. Oligonuclear Noble Metal Species......Page 1494
A. Cationic Species......Page 1499
B. Intramolecular CH Activation......Page 1503
C. Active Catalysts......Page 1505
A. Intermediates and Products from Ring-Opening Reactions......Page 1509
B. Direct Metalation of 2,2'-Bidipyrrins......Page 1514
VI. Fluorescent Boron Derivatives (OligoBODIPYs)......Page 1518
A. To Give Porphyrins......Page 1523
B. To Give Corroles and Other Porphyrinoids with a Direct Pyrrole–Pyrrole Bond......Page 1525
C. To Give Corrins and Hydroporphyrins......Page 1529
A. Tripyrrin- and Bai-Based Coordination Polymers......Page 1532
B. Bis(arylimino)isoindolines in Dendrimers......Page 1540
C. Tetrapyrroles in Supramolecular Assemblies......Page 1545
XI. References......Page 1547
Index to Volume 8
......Page 1565
Volume 9: Electronic Absorption Spectra - Phthalocyanines
......Page 1579
Contents......Page 1581
Preface......Page 1583
Contributing Authors......Page 1585
Contents of Volumes 1–10......Page 1593
42 / UV-Visible Absorption Spectroscopic Properties of Phthalocyanines and Related Macrocycles Takamitsu Fukuda and Nagao Kobayashi......Page 1599
List of Abbreviations......Page 1600
I. Introduction......Page 1601
II. Basic Theoretical Description of the Absorption Properties of Phthalocyanines......Page 1604
A. H2Pc and HPc......Page 1610
B. Group 1: Li2Pc, LiHPc, LiPc, Na2Pc and K2Pc......Page 1615
C. Group 2: BePc, MgPc, CaPc and BaPc......Page 1619
D. Group 3: ScPc, ScPc2, YPc2 and Y2Pc3......Page 1622
E. Complexes of the Lanthanide Elements......Page 1626
F. Complexes of the Actinide Elements......Page 1635
G. Group 4: TiPc, ZrPc, ZrPc2 and HfPc......Page 1637
H. Group 5: VPc, NbPc and TaPc......Page 1640
I. Group 6: CrPc, MoPc and WPc......Page 1643
J. Group 7: MnPc, TcPc, RePc and RePc2......Page 1647
K. Group 8: FePc, RuPc and OsPc......Page 1652
L. Group 9: CoPc, RhPc and IrPc......Page 1663
M. Group 10: NiPc, PdPc and PtPc......Page 1666
N. Group 11: CuPc, AgPc and AuPc......Page 1670
O. Group 12: ZnPc, CdPc, Cd2Pc3 and HgPc......Page 1672
P. Group 13: B-subPc, AlPc, GaPc, InPc and TlPc......Page 1676
Q. Group 14: SiPc, GePc, SnPc, SnPc2 and PbPc......Page 1684
R. Group 15: PPc, AsPc, SbPc, BiPc, BiPc2 and Bi2Pc3......Page 1693
IV. Collective Absorption Data Tables.......Page 1697
VI. References......Page 2200
Index to Volume 9
......Page 2243
Volume 10: Catalysis and Bio-Inspired Systems: Part 1
......Page 2252
Contents......Page 2254
Preface......Page 2260
Contributing Authors......Page 2262
Contents of Volumes 1–10......Page 2270
43 / Metalloporphyrin-Catalyzed Asymmetric Atom/Group Transfer Reactions Joshua V. Ruppel, Kimberly B. Fields, Nicole L. Snyder and X. Peter Zhang......Page 2276
I. Introduction......Page 2277
II. Epoxidation......Page 2278
A. Chiral Picket Fence Porphyrins......Page 2280
B. Chiral Strapped Porphyrins......Page 2301
C. Chiral Basket Handle Porphyrins......Page 2315
III. Cyclopropanation......Page 2318
A. Chiral Picket Fence Porphyrins......Page 2320
B. Chiral Strapped Porphyrins......Page 2339
IV. Aziridination......Page 2343
A. Chiral Picket Fence Porphyrins......Page 2344
1. Hydroxylation......Page 2348
2. Sulfoxidation......Page 2349
3. Amination......Page 2350
1. Hydroxylation......Page 2351
2. Sulfoxidation......Page 2352
VI. Conclusions......Page 2353
VIII. References......Page 2354
I. Introduction.......Page 2360
II. Iron(IV)-Oxo Porphyrin π-Cation Radical Complexes......Page 2368
III. Theoretical Modeling of CYP 450 Properties and Reactivities in Oxygenation Reactions......Page 2372
A. Compound I......Page 2373
B. Two-State Reactivity......Page 2381
C. Aliphatic C–H Activation by Cpd I of CYP 450......Page 2383
D. Aliphatic Hydroxylation Mechanisms with Byproduct Formation......Page 2395
E. Aromatic C–H Activation by Cpd I of CYP 450......Page 2400
F. C=C Epoxidation by Cpd I of CYP 450......Page 2402
G. Sulfoxidation by Cpd I of CYP 450......Page 2404
IV. Conclusions......Page 2406
VI. References......Page 2408
45 / On the Significance of Phthalocyanines in Solar Cells M. Victoria Martínez-Díaz and Tomás Torres......Page 2416
I. Introduction......Page 2417
II. Phthalocyanines in Organic Solar Cells......Page 2418
2. Hybrid Planar–Mixed Molecular Heterojunctions......Page 2421
3. Structural Modifications in the Phthalocyanines......Page 2423
4. Bilayer Heterojunctions Fabricated Using Two Different Processing Techniques......Page 2424
5. Tandem Solar Cells......Page 2425
B. Incorporation of Phthalocyanines into Organic Photovoltaic Devices by Solution Processing......Page 2428
III. Phthalocyanines as Sensitizers of Dye-Sensitized Solar Cells......Page 2432
A. Structural Optimization of Phthalocyanines......Page 2434
B. Insights into the Interfacial Electron Transfer Dynamics......Page 2441
C. The Role of Coadsorbents......Page 2442
D. The Cosensitization Strategy......Page 2444
IV. Summary and Conclusions......Page 2447
V. Acknowledgments......Page 2448
VI. References.......Page 2449
I. Introduction......Page 2458
II. Rational Design of Photosynthetic Reaction Center Models......Page 2459
III. Planar vs. Nonplanar Porphyrins......Page 2461
IV. Monomer vs. Dimer Porphyrins......Page 2465
V. Charge Separation Using Chlorophyll Analogs......Page 2471
VI. Multistep Photoinduced Electron Transfer......Page 2478
VII. Supramolecular Porphyrin Complexes......Page 2487
VIII. Porphyrin–Nanocarbon Composites......Page 2496
IX. Porphyrin Solar Cells......Page 2506
XI. Acknowledgments......Page 2511
XII. References......Page 2512
47 / Anchoring of Porphyrins and Phthalocyanines on Conductors and Semiconductors for Use in Hybrid Electronics Florence Duclairoir and Jean-Claude Marchon......Page 2520
List of Abbreviations.......Page 2522
I. Introduction......Page 2523
A. Overview......Page 2524
a. TPP Derivatives......Page 2528
b. Modulation of the Linker Between the Surface and the Macrocycle......Page 2531
ii. Tripodal Anchoring Groups......Page 2534
d. Immobilization of Complex Porphyrin Systems......Page 2535
a. Coordination Bond Coupling......Page 2539
b. Click Coupling......Page 2540
A. Overview......Page 2542
1. Si–O Bonding of the Macrocycle......Page 2547
a. Hydrosilylation Reaction......Page 2549
b. Diazonium Salt Reaction......Page 2550
3. Sequential Grafting......Page 2551
A. Overview......Page 2553
b. Ester Linkage with Oxidized CNT......Page 2555
i. Direct Immobilization......Page 2556
ii. Click Coupling......Page 2558
i. Amide Coupling of the Spacer to the Macrocycle......Page 2560
ii. Ester Coupling of the Spacer to the Macrocycle......Page 2563
a. Coordination Bond Coupling......Page 2564
c. Crown Ether-Cation Coupling......Page 2565
3. Graphene Functionalization via Amide Linkage......Page 2567
4. Diamond Functionalization via C–C Linkage and Amide Coupling......Page 2568
A. Overview......Page 2569
b. Sequential Immobilization......Page 2570
2. Phosphonate Linkage......Page 2572
A. Overview......Page 2574
1. Molecular Capacitor Memory Cell......Page 2575
3. Hybrid Nanowire Transistor Memory......Page 2577
4. Molecular Break-Junction Device......Page 2578
VII. Conclusion......Page 2579
VIII. References......Page 2580
48 / Bioinspired Catalysts with B12 Enzyme Functions Yoshio Hisaeda and Hisashi Shimakoshi......Page 2588
List of Abbreviations......Page 2589
B. B12 Model Complexes......Page 2590
C. Construction of Artificial Enzymes......Page 2592
II. Bioinspired 1,2-Migration Reactions......Page 2594
A. 1,2-Migration of Functional Groups on Cobalt Complexes......Page 2595
1. Catalytic Simulation of Methylmalonyl-CoA Mutase......Page 2596
2. Catalytic 1,2-Migration of Functional Groups......Page 2599
3. Ring-Expansion Reactions......Page 2601
C. Artificial Enzymes Composed of Apoenzyme Model and B12 Model Complexes......Page 2602
1. Methylmalonyl-CoA Mutase-like Reactions......Page 2603
2. Glutamate Mutase-like Reactions......Page 2606
3. Other Carbon-Skeleton Rearrangement Reactions......Page 2608
A. Methyl Transfer to Alkylthiols......Page 2609
B. Methyl Transfer to Inorganic Arsenics......Page 2612
IV. Bioinspired Dehalogenation Reactions......Page 2613
A. Reduction of Organic Halides by B12 Derivatives......Page 2614
B. Electrocatalytic Reduction of Organic Halides by B12 Derivatives......Page 2619
C. Photocatalytic Reduction of Organic Halides by B12 Derivatives......Page 2621
D. Dechlorination of Organic Halides by Other Cobalt Complexes......Page 2624
B. Noncovalently Bound B12 Modified Electrodes......Page 2625
C. Polymer-coated B12 Modified Electrodes......Page 2627
D. Covalently Bound B12 Modified Electrodes......Page 2631
E. B12 Immobilized Polymers......Page 2632
A. Asymmetric Reactions......Page 2633
B. Other Reactions......Page 2636
VIII. References......Page 2639
Index to Volume 10
......Page 2646
Cumulative Index to Volumes 1–10......Page 2660