Organic Photochromic and Thermochromic Compounds

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1 Organic Photochromic and Thermochromic Compounds Volume 1: Main Photochromic Families Edited by John C. Crano Late of PPG Industries, Inc. Monroeville, Pennsylvania and Robert J. Guglielmetti University of Aix-Marseille II Marseille, France Plenum Press New York and London

Table of Contents Introduction 1. Aim and Organization of the Book 1 2. Brief Historical Survey of Photochromism 2 3. Definitions of Photochromism 2 4.

2 Table of Contents Introduction 1. Aim and Organization of the Book 1 2. Brief Historical Survey of Photochromism 2 3. Definitions of Photochromism 2 4. Brief Analysis of the Different Chapters and their Main Topics 4 5. Conclusion and Future Developments 8 6. References 9 1. Spiropyrans Robert C. Bertelson 1.1. Introduction Synthesis General Summary Intermediates for Spiropyrans Fischer's Base Syntheses Fischer's Base Salts by Alkylation of Indolenines Fischer's Bases from Oxindoles Fischer's Bases by Oxidation of Indolines Substitution in Fischer's Bases Preparations of Indolenines Preparation of Indoles Preparations of Spiropyrans Substitution in Spiropyrans New Materials. Properties and Structure-Property Relationships Spiropyrans in Fluid Solutions Spiropyrans with Long-wavelength Absorption Spiropyrans as Vapor-Deposited and Amorphous Films Polymeric Spiropyrans 57 xv

xvi Table of Contents 1.3.5. Spiropyran Aggregates 59 1.3.6. Mechanistic Studies: Photocoloration, Photodecoloration, Fatigue and Photodegradation 60 1.3.7.

3 xvi Table of Contents Spiropyran Aggregates Mechanistic Studies: Photocoloration, Photodecoloration, Fatigue and Photodegradation Reactions of Spiropyrans with Inorganic Reagents Spiropyrans in Sol-Gel Matrices Quantum Mechanical Calculations Optically Active Spiropyrans Applications and Future Trends Some Representative Preparations NitroBIPS Phenyl Fischer's Base and its Hydroiodide Formylsalicylaldehyde References Spirooxazines Shuichi Maeda 2.1. Introduction Structure, Synthesis, and Photochromic Properties Substitution on the Naphthoxazine Ring Moiety Substitution on the Indoline Ring Moiety Other Indolinospirooxazines Miscellaneous Spirooxazines Chelation of Spirooxazine Derivatives Crowned Spirooxazines Electropolymerization of Spironaphthoxazine-Thiophene Derivatives Molecular Structure and Mechanism of the Photochromic Reactions Nature of the Closed Form Nature of the Colored Form Mechanism of the Photochromic Reactions Applications Stabilization of Spirooxazines Commercial Plastic Photochromic Lenses Microencapsulated Photochromic Ink Photochromic Lamiglass Synthesis Examples Synthesis of l,3,3-trimethylspiro[indoline-2,3'-[3h]naphth]- [2,16][l,4]oxazine] (Compound 1) Synthesis of 6'-indolino-l,3,3-trimethylspiro[indoline-2,3'-[3H]- naphth[2,l-6][l,4]oxazine] (Compound 7) Synthesis of r,3',3'-trimethylspiro[3tf-naphth][2,l-6][l,4]- oxazine-3,2'-piperidine (Compound 16) 106

Table of Contents xvii 2.5.4. Synthesis of Compound 19 107 2.6. References 107 3. Benzo and Naphthopyrans (Chromenes) Barry Van Gemert 3.1. Introduction Ill 3.1.1. Definition Ill 3.1.2. Historical Perspective Ill 3.

4 Table of Contents xvii Synthesis of Compound References Benzo and Naphthopyrans (Chromenes) Barry Van Gemert 3.1. Introduction Ill Definition Ill Historical Perspective Ill Current Review Photochromic Mechanism Performance Testing Fatigue Testing Fatigue Specific to Pyrans Stability and Stabilization #-Naphtho[2,l-%yrans Nomenclature Structure-Photochromic Activity Relationships Substitution at the 1- and 2-Positions Substitution at the 3-Position Pyran Substitution via Heteroaromatic Annellation Substitution at the 5-Position Substitution at the 6-Position Substitution at the 8-Position Substitution at the 7, 9, and 10-Positions General Note #-Naphtho[l,2- >]pyrans Nomenclature Substituent Effects Substitution at the 2-Position Substitution at the 5-Position #-Naphtho[2,3-6]pyrans #-l-Benzopyrans (Chromenes) General Substituent Effects Synthetic Methods Preparation of 3,3-Diphenyl-3#-naphtho[2,l-ft]pyran Preparation of 2-Methyl-7,7-diphenyl-7#-pyranol[2,3-g]- benzothiazole Preparation of 2,2'-Spiroadamantylidene-2#-naphtho[ 1,2-6]- pyran Concluding Remarks References 137

xviii Table of Contents 4. Fulgide Family Compounds: Synthesis, Photochromism, and Applications Mei Gong Fan, Lianhe Yu, and Weih Zhao 4.1. Introduction 141 4.2.

5 xviii Table of Contents 4. Fulgide Family Compounds: Synthesis, Photochromism, and Applications Mei Gong Fan, Lianhe Yu, and Weih Zhao 4.1. Introduction Fulgides with Aromatic Ring Systems Phenyl Fulgides Nuclear Magnetic Resonance Spectroscopy X-Ray Crystallography UV-Visible Spectroscopy Photochromic Reactions, Substituent Effects and Fatigue Resistance of Phenyl Fulgides Miscellaneous Aryl Aromatic Fulgides Fulgides with Heterocyclic Ring Systems Furyl Fulgides Substituent Effects on the Quantum Yield of Photochromic Reactions of Furyl Fulgides oc-alkyl Substituent Effects on the Photochromism of Furyl Fulgides Steric Effects on the Photochromic Behavior of the Alkylidene Group of Furyl Fulgides Comprehensive Steric Effect on the Quantum Yield of the Photoreactions of Furyl Fulgides Photochromism of Furyl Fulgides in Polymer Matrices Crystal Structures of Furyl Fulgides Helical Chirality of Furyl Fulgide Thienyl Fulgides Indolyl Fulgides Pyrryl Fulgides Absorption Spectra of Fulgide 62 and its Colored Form (63) The Effect of Solvent Polarity on the Absorption Spectra of Fulgide 62 and its Colored Form (63) Substituent Effects on the Absorption Spectra of Pyrryl Fulgide 62 and Colored Forms (63) Crystal Structure of Fulgide 62n Heteroaromatic Fulgides Containing two Hetero Atoms Fulgimides, Isofulgimides, Fulgenates, Fulgenolides and Dicyanomethylene Derivatives of Fulgides Fulgimides Isofulgimides Fulgenates and Fulgenolides Tetrahydrofuran-2-one Derivatives Photochromic Mechanism Chromophores and Excited States of Fulgides E > Z Isomerization 186

Table of Contents xix 4.5.3. Photocyclization Reactions of Fulgides and Derivatives 190 4.5.4. Heliochromic Reaction 194 4.6. Applications of Fulgides and their Derivatives 195 4.6.1. Optical Storage 195 4.

6 Table of Contents xix Photocyclization Reactions of Fulgides and Derivatives Heliochromic Reaction Applications of Fulgides and their Derivatives Optical Storage Actinometry Photochromic Inks, Paints and Fabrics Applications in Other Advanced Materials Some Examples of Detailed Syntheses References Diarylethenes with Heterocyclic Aryl Groups Masahiro Irie 5.1. Introduction Synthesis Diarylperfluorocyclopentenes Diarylmaleic Anhydrides Properties Thermal Stability Fatigue-Resistant Character Absorption Spectra Response Time Molecular Systems with Controlled Functionality Gated Reactivity Photoswitching of Electrochemical Properties Conclusion References Photochromism of Dihydroindolizines and Related Systems Heinz Dürr 6.1. Introduction Syntheses of Photochromic Molecules Based on a 1,5-Electrocyclic Reaction Type 2 System Cyclopropene: Route (a) Pyrazole Route (b) Retro-1,5-Electrocyclization: Route (c) Diazo: Route (d) Tetrahydro- and Hexahydroindolizines Biphotochromic Systems Route 1: Type a and Type b Systems Type с Systems 229

XX, Table of Contents 6.3. Photochromic Systems with One Heteroatom 231 6.3.1. Spectra of the Colorless and the Colored Forms 231 6.3.2. Spectra of Colored Forms 233 6.3.3. Solvent Effects on the Colored Forms 234 6.

7 XX, Table of Contents 6.3. Photochromic Systems with One Heteroatom Spectra of the Colorless and the Colored Forms Spectra of Colored Forms Solvent Effects on the Colored Forms Thermal Reactions in Solution/Structure Fading Rate Relationships Modified Systems: Tetra and Hexahydroindilizines Mechanism of Photocoloration Quantum Yield of Photocoloration and Photobleaching Photochromic Systems Based on Pentadienyl Anions with Two Heteroatoms Type 1,2 Systems Type 2,3 Systems Photochromic Systems Based on Pentadienyl Anions with Three Heteroatoms Supramolecular and Environmental Effects and Applications Supramolecular Systems Photochromic Systems in Liquid Crystalline Phase Photochromic Systems in Polymers DHI Dissolved in Polymers Polymer-Linked Systems IR-Sensitive Materials Description of Apparatus Syntheses of Key Examples Conclusions References Photochromic Quinones Valeri Barachevsky 7.1. Introduction Synthesis of Photochromic Quinones Methylnaphthoquinone Derivatives of Anthraquinone Derivatives of Naphthacenequinone Phenoxypentacenequinone and Derivatives of Phthaloylpyrene Mechanism of Photochromic Transformations in Quinones Photochromism of Naphthoquinone Photochromism of Anthraquinones Alkylanthraquinones Acyloxyanthraquinones Aryloxyanthraquinones Anthrapyridones and Anthrapyridines Pyrazoloanthrones 284

Table of Contents xxi 7.3.3. Photochromism of Naphthacenequinones 285 7.3.3.1. Aryloxynaphthacenequinones 285 7.3.3.2. Naphthacenepyridones and Naphthacenepyridines... 288 7.3.3.3. Pyrone 288 7.3.3.4.

8 Table of Contents xxi Photochromism of Naphthacenequinones Aryloxynaphthacenequinones Naphthacenepyridones and Naphthacenepyridines Pyrone Pyrazolonaphthacenones Photochromism of Phenoxypentacenequinone and Derivatives of Phthaloylpyrene Photochromic Behavior of Quinones Spectral Characteristics Kinetic Characteristics Methylnaphthoquinone Derivatives of Anthraquinone Derivatives of Naphthacenequinone Fatigue Methylnaphthoquinone Derivatives of Anthraquinone Derivatives of Naphthacenequinone Applications of Photochromic Quinones Recording and Multiplication of Images Optical Memory Gradation Masking Conclusion Examples of Synthesis of Photochromic Quinones l-phenoxy-2,4-dioxy and l-(p tert-butyl)phenoxy-2,4- dioxyanthraquinones Phenoxy-5,12-naphthacenequinone Phenoxy-5,12-pentacenequinone l,3-dichloro-6-phenoxy-7,12-phthaloylpyrene References Perimidinespirocyclohexadienones Vladimir Minkin, Vitaly Komissarov, and Vladimir Kharlanov 8.1. Introduction Synthesis and Reactions Spectral and Photochromic Properties Thermal Decoloration Reaction Thermo- and Solvatochromism Integrated Photochromic and Electrochromic Properties Photoinitiated Interconversion of Ring-Chain Isomers of bis-quinone Imines Derived from Aromatic Diamines Preparative Procedures ,3-Dihydro-2-spiro-4'-(2',6'-dWert-butylcyclohexadien-2',5'- one) perimidine, la (R = H) 337

XXÜ Table of Contents 8.8.2. l-methyl-2,3-dihydro-2-spiro-4'-(2',6'-di-?ert-butylcyclohexadien-2',5'-one) perimidine, la (R = CH 3 ) 338 8.8.3. 2,3-Dihydro-2-spiro-4'-[(4//)-2',-ter/-butylnaphthalen-l'- one]perimidine, 4 (R,R',RR" = H) 338 8.

9 XXÜ Table of Contents l-methyl-2,3-dihydro-2-spiro-4'-(2',6'-di-?ert-butylcyclohexadien-2',5'-one) perimidine, la (R = CH 3 ) ,3-Dihydro-2-spiro-4'-[(4//)-2',-ter/-butylnaphthalen-l'- one]perimidine, 4 (R,R',RR" = H) ,7,9-Trimethyl-2,3-dihydro-2-spiro-4'-(2',6'-di-?ert-butylcyclohexadien-2',5'-one)-pyrido-[4,3,2-d,e]quinazoline, 9 (R' = H, R = Me, Ar=H) References Photochromism by Electron Transfer: Photochromic Viologens Masata Nanasawa 9.1. Introduction to Photochromism by Electron Transfer Photochromism of Viologens Introduction General Synthetic Methods Photochromic Behavior Effect of Matrices on Photochromism A Variety of Color Species of Viologens Photochromism of Molecular Assembly Viologen Bearing a Metal Complex as Counteranion Applications Photochromism of Thiazines Introduction Photochromic Properties Applications Thiazine Dyes Effect of the Kind of Reductants Effect of Coating Substrate References 367 Index 371

Organic Photochromic and Thermochromic Compounds. Volume 1: Main Photochromic Families

Organic Photochromic and Thermochromic Compounds Volume 1: Main Photochromic Families TOPICS IN APPLIED CHEMISTRY Series Editors: Alan R. Katritzky, FRS University of Florida Gainesville, Florida Gebran