Photochromism: Molecules and Systems (eBook)

Front Cover 1
Photochromism: Molecules and Systems 4
Copyright Page 5
Table of Contents 16
Preface (1990 Edition) 6
Foreword (2003 Revised Edition) 8
Preface (2003 Revised Edition) 10
See Literature Survey Updates (1989 – 2001) 14
General Definitions ORGANIC PHOTOCHROMISM: IUPAC A TECHINICAL REPORT ON CLASSES AND TERMS USED IN PHOTOCHROMISM 28
Part 1: General Introduction 56
Chapter 1. General Introduction 56
1. Organization of the Book 56
2. Brief Historical Survey of Photochromism 58
3. Definition of Photochromism 60
4. Outlook and Future Developments 65
References 69
Part 2: Photophysical, Photochemical and Photokinetic Properties of Photochromic Systems 70
Chapter 2. Photophysical, Photochemical and Photokinetic Properties of Photochromic Systems 70
1. Photophysical Properties 70
2. Photochemical properties 76
3. Photokinetics Applied to Photochromism 79
4. Concluding Remarks 115
References 116
Addendum Photochromism based on triplet-triplet absorption 118
Part 3: Photochromism Based on "E-Z" Isomerization of Double Bonds 119
Chapter 3. Cis-Trans Isomerization of C=C Double Bonds 119
1. Introduction 119
2. Generalizations 121
3. Stilbene 123
4. Diphenylpolyenes 169
5. Rotamerism 198
6. Concluding Remarks 208
Acknowledgement 208
References 209
Addendum Photochromism based on eis-trans isomerization/indigo derivatives 218
Chapter 4. AZO Compounds 220
1. Introduction 220
2. Special Features 221
3. Isomerization 227
4. Application of Photochromism of Azo Compounds 241
5. Summary 242
References 243
Part 4: Photochromism Based on Pericyclic Reactions: Electrocyclization Reactions 248
Chapter 5. 4n Systems Based on 1,3-Electrocyclization 248
1. Introduction 248
2. Stereochemistry in 1,3-Electroyclic Reactions 249
3. Oxiranes 250
4. Aziridines 254
5. Nitrones 260
6. Azomethinimines 262
7. Applications of Photochromic Three-membered Heterocycles 263
8. Concluding Remarks 263
References 264
Chapter 6. 4n+2 Systems Based on 1,5-Electrocyclization 265
1. Introduction 265
2. Theoretical Studies of 1,5-Electrocyclization 268
3. Photochromism Based on Pentadienyl Anions with One Heteroatom 272
4. Thermal Reactions in Solution 287
5. Photoreactions/Deactivation Channels of Type-2-System 291
6. Photochromic Systems Based on Pentadienyl Anions with Two Heteroatoms 300
7. Photochromic Systems Based on Pentadienyl Anions with Three Heteroatoms 308
8. Environmental Effects and Application 310
9. Syntheses of Photochromic Molecules Based on the 1,5-Electrocyclic Reaction 315
References 321
Chapter 7. 4n+2 Systems: Molecules Derived from Z-Hexa-1,3,5-Triene/ Cyclohexa- 1,3-Diene 325
1. Introduction 325
2. All-Carbon Systems 334
3. Systems with Heteroatoms 355
References 364
Chapter 8. 4n+2 Systems: Spiropyrans 369
1. Introduction 369
2. Spectrokinetic Properties of Photochromic Interconversions in Solution 378
3. Structural and Theoretical Studies Coordination Chemistry
4. Photochemical and Photophysical Studies of Photochromic Inter-conversion, Photocoloration and Photodegradation 453
5. Synthetic Routes to Spiropyrans or Derived Compounds 472
6. Concluding Remarks 507
Acknowledgement 509
References 510
Chapter 9. 4n+2 Systems: Fulgides 522
1. Introduction 522
2. Phenyl Fulgides 530
3. Fatigue Resistance 536
4. Steric Effects 541
5. Concluding Remarks 545
References 546
Chapter 10. 4n+2 Systems: Spirooxazines 548
1. Introduction 548
2. Spectral Properties 550
3. Thermochromism of Spirooxazine Compounds 557
4. Kinetics of the Thermal Fading 560
5. Photochemical Properties 560
6. Synthetic Methods 561
7. Addenda 563
References 563
Chapter 11. 4n and 4n+2 Systems (n> 2) Based on 1,7- and 1,10-Electrocyclization
1. Introduction 565
2. 4n Systems (n> 2): 1,7-Electrocyclizations
3. 4n+2 Systems (n> 2): 1,10-Electrocyclizations
References 568
Part 5: Photochromism Based on Pericyclic Reactions: Cycloaddition Reactions 569
Chapter 12. Cycloaddition Reactions Involving 4n Electrons: (2+2) Cycloaddition Photochemical Energy Storage Systems Based on Reversible Valence Photoisomerization
1. Introduction 569
2. (2+2) Addition: Direct and Triplet Sensitized Photorearrangement 573
3. (2+2) Addition: Pathways Involving Electron Transfer or Excited Complexes 577
4. (2+2) Reversion: Reactivity of Small Ring Radical Cations 583
5. Concluding remarks: Future Directions 587
Acknowledgements 591
References 591
Chapter 13. Cycloaddition Reactions Involving 4n Electrons: (2+2) Cycloaddition Molecules with Multiple Bonds Incorporated in or Linked to Aromatic Systems
1. Introduction 594
2. Intermolecular (2+2) Photocycloaddition 597
3. Intramolecular (2+2) Photoaddition 606
4. Summary and Conclusion 612
Acknowledgements 612
References 613
Chapter 14. Cycloaddition Reactions Involving 4n Electrons: (4+4) Cycloaddition Reactions between Unsaturated Conjugated Systems 616
1. Introduction 616
2. Mechanism of Photodimerimtion and Cycloreversion 619
3. Intermolecular (4+4) Photocycloaddition 628
4. Intramolecular (4+4) Photocycloaddition 653
5. Summary and Conclusion 676
Acknowledgements 677
References 677
Chapter 15. Cycloaddition Reactions Involving 4n+2 Electrons. Photochromism Based on the Reversible Reagtion of Singlet Oxygen with Aromatic Compounds 686
1. Introduction 686
2. Results of Theoretical Investigations on the Formation Reaction and the Chemical Behaviour of Endoperoxides 687
3. Structural Formulas 690
4. Experimental Results on the Chemistry of Endoperoxides 690
5. Photochromic Systems of High Reversibility Based on the Reversible Photooxygenation of Aromatic Compounds 696
6. Conclusions 706
References 708
Part 6: Photochromism Based on Tautomerism (Hydrogen Transfer) 709
Chapter 16. Tautomerism by Hydrogen Transfer in Salicylates, Triazoles and Oxazoles 709
1. Introduction 709
2. Förster Cycle 710
3. Methyl Salicylate 714
4. Tunnel Effect 718
5. 2-(2'-Hydroxyphenyl) benzotriazole and Related Compounds 720
References 736
Chapter 17. Tautomerism by Hydrogen Transfer in Anils, Aci-Nitro and Related Compounds 740
1. Anil tautomerism 740
2. Aci-Nitro Phototautomerism 757
3. Other H-transfer Phototautomerism 761
Acknowledgement 765
References 765
Part 7: Photochromism Based of Dissociation Processes 768
Chapter 18. Photochromism Based on Dissociation Processes 768
1. Introduction 768
2. Photochromism based on Homolytic Dissociation Processes 769
3. Photochromism Based on Heterolytic Dissociation Processes 782
References 789
Chapter 19. Phytochrome 793
1. Introduction 793
2. Phytochrome 794
3. Concluding Remarks 807
Acknowledgements 808
References 809
Chapter 20. Retinal Proteins 811
1. Introduction 811
2. The Chromophore: Retinal, Unprotonated and Protonated Retinylidene Schiff Base 814
3. Visual Pigments 817
4. Retinal Proteins of Halobacterium Halobium 827
5. Concluding Remarks 839
References 840
Part 8: Environmental Effects on Organic Photochromic Systems 848
Chapter 21. Environmental Effects on Organic Photochromic Systems 848
1. Introduction 848
2. Indolinobenzospiropyrans 848
3. Aromatic Azo Compounds 870
4. Conclusion 873
References 875
Part 9: The Use of Silver Salts for Photochromic Glasses 877
Chapter 22. The Use of Silver Salts for Photochromic Glasses 877
1 .Introduction 877
2. Fundamental Technical Properties of Photochromic Glasses doped with Silver Halides 878
3. Compositions of Photochromic Glasses 881
4. Origin of the Induced Absorption Effect 887
5. Reaction Kinetics of the Induced Absorption Coefficient 890
6. Thermal and Optical Regeneration 897
7. Implications and Discussion of the Reaction Kinetics 900
8. An Atomic Model of the Darkening and Regeneration Kinetics of Photochromic Glasses and Open Questions 903
9. Summary and Concluding Remarks 907
Acknowledgements 907
References 908
Part 10: Applications 910
Chapter 23. Spiropyrans and Related Compounds 910
1. Introduction and Classification of Applications 910
2. An Autoprocessor Reprography System Using Photochromic Spiropyrans or Merocyanines 919
3. A potential Application of Spiropyran Derivatives in Thermographic Recording Process 926
References 931
Chapter 24. Spirooxazines 934
1. Light Filters 934
2. Applications Other than Light Filters 936
References 936
Chapter 25. Actinometry 938
1. Comparison to Physical Measurements 938
2. Kinetic Principles in Actinometry 940
3. Photochromic Systems Embedded in Polymers 951
References 956
Chapter 26. Photochromic Materials and Photoresists 958
1. Introduction 958
2. Photochromic Micelles and Vesicles 959
3. Photochromic Liquid Crystals 962
4. Photochromic Polymer Liquid Crystals 965
5. Two-photon Radical Photoinitiators 967
6. Dual Mode Photoresists 968
7. Contrast Enhanced Layer (CEL) 970
8. Conclusion 972
References 972
Part 11: New Developments Highly Promising for Applications 974
Chapter 27. Photochromism by Orientation 974
1. Introduction 974
2. The Principles 975
3. Photoinduced Orientation 979
4. Examples of Photochromism by Orientation 982
Acknowledgement 984
References 984
Chapter 28. Spectral Hole-Burning 985
1. Introduction 985
2. Principles of Spectral Hole-burning 987
3. Detection of Spectral Holes 993
4. Properties of Spectral Holes 998
5. Optical Information Storage 1003
6. Conclusions 1005
References 1006
Chapter 29. Bacteriorhodopsin and its Functional Variants: Potential Applications in Modern Optics 1009
1. Introduction 1009
2. Structure and Function of Bacteriorhodopsin 1010
3. Bacteriorhodopsin Variants 1013
4. Optical Applications of BR-Wild Type and BR-326 1015
Acknowledgements 1027
References 1028
Glossary of Terms 1031
Chapter 30. Glossary of Terms Used in Photochemistry 1031
Appendix of Literature Updates 1088
Additional Literature Chapter 4 – Azo-compounds 1088
Additional Literature Chapter 6 – Dihydro-indolizines 1106
Additional Literature Chapter 7 – Diarylethanes 1110
Additional Literature Chapter 8 – Chromenes 1120
Additional Literature Chapter 8 – Naphthopyrans 1128
Additional Literature Chapter 8 – Spiropyrans 1138
Additional Literature Chapter 9 – Fulgides 1162
Additional Literature Chapter 9 – Fulgirnides 1174
Additional Literature Chapter 10 – Spirooxazines 1176
Additional Literature Chapter 10 – Spiroxazines 1184
Additional Literature Chapter 14 – Anthracenes 1186
Additional Literature Chapter 16 – Hydrogen Transfer 1190
Literature Survey on Spiroperimidines – Chapter 16 1192
Additional Literature on Anils – Chapter 17 1194
Literature on Group Transfer Photochromism of Quinones – Chapter 17 1198
Literature Survey for Photochromism based on Electron Transfer of Bipyriddinium-salts (Viologenes) Chapter 17 1202
Literature Survey on Photochromism of Triarylmethanes – Chapter 18 1206
Subject Index 1208