4Table 4.1 Photocyclization and photocycloreversion quantum yields inn‐hexane ...
4 Chapter 6Table 6.1 Magnetic interactions between two nitronyl nitroxide radicals in di...
5 Chapter 8Table 8.1 Examples of polymers having diarylethene units in the main chain.Table 8.2 Examples of polymers having diarylethene units in the side groups.
6 Chapter 9Table 9.1 Photophysical and photochemical properties of turn‐on mode fluoresc...Table 9.2 Photochemical and photophysical properties of8.Table 9.3 Radiation‐induced coloration of diarylethene3 in solutions and soli...
List of Illustrations
1 Chapter 1Figure 1.1 The use of light in biological systems.Scheme 1.1 Molecular photoswitches and years when they were discovered.Figure 1.2 Schematic illustration of the photoinduced conformational change ...Figure 1.3 A synthesis route of poly(2,3‐diphenylbutadiene) and its photoche...Figure 1.4 (A) Synthesis of polymers having (a) 2,3‐dimesitylbutene units an...Figure 1.5 Development of diarylethene molecular photoswitches.Figure 1.6 Color changes of diarylethene derivatives 1–7 in toluene up...Figure 1.7 Chemical structures and absorption spectra of open‐ and closed‐ri...Figure 1.8 (a) Chemical structures of open‐ and closed‐ring isomers of 8. (b...
2 Chapter 2Scheme 2.1 Electrocyclic reactions of diarylethenes 9−12.Scheme 2.2 Disrotatory and conrotatory cyclization reactions of hexatriene....Figure 2.1 State correlation diagrams for the electrocyclic reactions in dis...Figure 2.2 State correlation diagrams for the electrocyclic reactions in con...Figure 2.3 Correlation between the ground state energy difference between op...Scheme 2.3 The structure changes of phenyl and five‐membered heterocyclic ri...Figure 2.4 Thermal stability of diarylethene derivatives. Any appreciable ch...Figure 2.5 Potential energy surfaces of a model diarylethene.Figure 2.6 Potential energy surfaces of ground (1A) and two excited (2A and ...Figure 2.7 Schematic representation of the structures of S 0 (orange) and S 1 ...Figure 2.8 Outline of two reaction paths corresponding to ring‐opening and r...Scheme 2.4 A diarylethene open‐ring isomer has two conformations with two ar...Figure 2.9 Transient absorption spectra of 5 during the ring‐closing reactio...Figure 2.10 Transient absorption spectra of 5 during the ring‐closing reacti...Figure 2.11 Time profiles of transient absorbance of 13 in n‐hexane excited ...Figure 2.12 Time‐resolved transient absorption spectra of 20c in n‐hexane ex...
3 Chapter 3Figure 3.1 1H NMR methyl signals of (a) 5o and (b) 13o in CDCl3.Scheme 3.1 A diarylethene derivative having a benzobis(thiadiazole) bridge. ...Figure 3.2 (a) Chemical structures of open‐ and close‐ring isomers of 64. (b...Figure 3.3 Schematic illustration of the solvent effect on the photocyclizat...Figure 3.4 Photoirradiation wavelength dependence of the cycloreversion quan...Figure 3.5 (a) Quantum yields for the ring‐opening reaction of 67c as a func...Figure 3.6 Correlation between the cycloreversion quantum yield of diarylper...Figure 3.7 Thermal stability of closed‐ring isomers. The values below the mo...Figure 3.8 (a) F o − F c difference Fourier electron density maps through peak...Figure 3.9 ORTEP drawing of by‐product 88 showing 50% probability displaceme...Scheme 3.2 Two routes (1 and 2) of the byproduct formation.Figure 3.10 The fatigue resistant property of diarylethene derivatives. Init...Figure 3.11 Schematic representation of structures of the S 0 (orange) and S 1 Figure 3.12 Average ΔOD of 5 for the first 3 × 104 cycles binned in 1 × 104 ...Figure 3.13 Fluorescence quenching of 126 based on a Förster‐type intramolec...Scheme 3.3 Chemical structures of (a) dithienylethenes–perylenemonoimide com...Figure 3.14 (a) Chemical structures of 137o and 137c. (b) Fluorescence inten...Scheme 3.4 Photoisomerization of fluorescent diarylethenes 138–142 and...Figure 3.15 (a) Absorption spectra of 8o (black dashed line), 8c (black soli...Figure 3.16 Photographs of 1,4‐dioxane solutions containing 8 and 142 before...Scheme 3.5 Photocyclization reactions of P ‐ and M ‐helical open‐ring conforme...Scheme 3.6 Chiral diarylethenes 143 and 144.Scheme 3.7 Chiral (145, 150, 154) and achiral (146, 147, 148) diarylethenes ...Figure 3.17 Chiral switch 149, which has (R)‐1‐phenylethylamine‐derived amid...Figure 3.18 Molecular modeling concept and the molecular design of chiral di...Scheme 3.8 Diastereospecific photoisomerization reactions of 152 and 153.
4 Chapter 4Figure 4.1 A synthetic route of diarylethene 156 having oligothiophene aryl ...Figure 4.2 Color changes of several diarylethene single crystals upon photoi...Scheme 4.1 Examples of diarylethene derivatives, which undergo photoswitchin...Figure 4.3 (a) Shape of single crystal 3 and (b) directions of long (x) and ...Figure 4.4 Polarized absorption spectra of the red color in single crystal 3 Figure 4.5 Photographs of single crystal 158 under polarized light before ((...Figure 4.6 Polarized absorption spectra of colored single crystal 158 (surfa...Figure 4.7 F o – F c difference Fourier electron density maps for single cryst...Figure 4.8 ORTEP drawings of photoirradiated crystal 3. Black and red molecu...Figure 4.9 Molecular structures of the closed‐ring isomer 3c (a) generated i...Figure 4.10 Relationship between the photocyclization quantum yield and the ...Scheme 4.2 Dithienylethenes having anthracene substituents.Figure 4.11 (a) Three dithienylethenes 167, 4, and 20, which have similar si...Figure 4.12 (a) Molecular structure of 168. (b) ORTEP drawings and (c) molec...Figure 4.13 Photographs of single crystals of (a) 169o and (b) 170o. Top: ph...Figure 4.14 Patterned fluorescence photoswitching of single crystal 170o. (a...Figure 4.15 (a) Structures of open‐ and closed‐ring isomers of 5. (b) AFM im...Figure 4.16 Deformation of single crystals upon irradiation with UV (365 nm)...Figure 4.17