Читать книгу Diarylethene Molecular Photoswitches - Masahiro Irie - Страница 4

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 Molecular packing of open‐ring isomers of 1,2‐bis(2‐ethyl‐5‐phen...Figure 4.18 Chemical structures of open‐ and closed‐ring isomers of 1,2‐bis(...Figure 4.19 (a) Chemical structures of open‐ and closed‐ring isomers of 1,2‐...Figure 4.20 A shot of a tiny silica‐particle (∼100 μm) by crystal‐rod of 4 u...Figure 4.21 (a) Chemical structures of component diarylethenes 172 and 173 i...Figure 4.22 (a) Photomechanical work of a molecular crystal cantilever made ...

5 Chapter 5Figure 5.1 (a) Fluorescence photoswitching of dyad 126 upon alternate irradi...Figure 5.2 Histograms of (a–c) on time and (d–f) off time in PnBMA (a, d), P...Figure 5.3 A schematic diagram of the potential energy surfaces of a diaryle...Figure 5.4 Single‐molecule fluorescence photoswitching in a poly(methyl acry...Figure 5.5 Near‐field optical recording on an amorphous film of 178. Thickne...Figure 5.6 The images of an amorphous film of diarylethene 180 irradiated wi...Figure 5.7 Holographic recording on a PMMA film containing 181 based on a po...Figure 5.8 (a) Chemical structures of open‐ and closed‐ring isomers of 182. ...Scheme 5.1 Refractive index changes (Δn) of diarylethene derivatives at 817 ...

6 Chapter 6Figure 6.1 One‐way switching of conductance from the on state to the off sta...Figure 6.2 Photoswitching of conductance of diarylethene derivatives inserte...Figure 6.3 (a) A mixed self‐assembled monolayer, which incorporates dodecane...Figure 6.4 Configuration of the Mach–Zehnder modulator using diarylethene 13 Figure 6.5 The open‐ring (191o) and closed‐ring (191c) isomers of radical‐su...Scheme 6.1 Open‐ring (192o) and closed‐ring (192c) isomers of radical‐substi...Scheme 6.2 Open‐ring (193o, 194o, 195o, 196o) and closed‐ring (193c, 194c, 1...Figure 6.6 ESR spectral changes for 193 (n = 1) along with photoisomerizatio...Figure 6.7 Photoisomerization of diarylethene dyad 197 upon photoirradiation...Figure 6.8 ESR spectra of (a) 197 (OO), (b) 197 (CO), and (c) 197 (CC).

7 Chapter 7Figure 7.1 (a) Schematic illustration of the fabrication procedure of the cr...Figure 7.2 Schematic illustration of the fabrication procedure of the crysta...Figure 7.3 (a) Selective metal deposition on the UV‐irradiated colored surfa...Figure 7.4 (a) μ‐Fuse and its operation. (b) Current–voltage characteristics...Figure 7.5 (a) Scheme of absorption modulation. Absorption at λ ₁ makes ...

8 Chapter 8Scheme 8.1 Examples of synthetic methods of polymers having diarylethene uni...Scheme 8.2 Synthesis of polymer p12 by oxidation polymerization of diaryleth...Scheme 8.3 Selective photoreactions of polyurethanes p56 containing two kind...Scheme 8.4 (a) Diarylethene dopants for liquid crystals. (b) A diarylethene ...

9 Chapter 9Figure 9.1 Two types (a and b) of structures of organic field‐effect transis...Scheme 9.1 Chemical structures of (a) polymeric and (b) small‐molecule semic...Figure 9.2 3D framework structures of photoresponsive metal organic framewor...Figure 9.3 The metal organic cage composed of two Pd²⁺ ions and four bis...Scheme 9.2 Turn‐on mode fluorescent diarylethene derivatives.Figure 9.4 Fatigue‐resistant property of sulfone derivatives of 1,2‐bis(2‐al...Figure 9.5 (a) Logarithmic plots of molar absorption coefficients of 8o in n...Figure 9.6 RESOFT and confocal images of Vero cells. The line profiles of re...Figure 9.7 STORM images of Vero cells acquired (A) with and (B) without UV a...Figure 9.8 Fatigue resistance of diarylethene 216 in an aqueous phosphate bu...Scheme 9.3 Rearrangement of positions of single and double bonds in (a) Diel...Scheme 9.4 The molecular design principle of photoresponsive polymers having...Scheme 9.5 Photocontrol of formation and scission of bonds using diarylethen...Scheme 9.6 Examples of biologically active diarylethene derivatives.Scheme 9.7 (a) Diarylethene crystal 3, which turned red upon γ‐rays irradiat...Figure 9.9 Fluorescence intensity increase upon γ‐irradiation. (a) Dependenc...