• Title/Summary/Keyword: cis-trans photoisomerization

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Preparation and Photophysical Properties of 4-(9-Anthrylethenyl)-4'-methyl-2,2'-bipyridine and Its Ruthenium Bipyridyl Complex $[Ru(bpy)_2(t-aemb)](PF_6)_2$

  • 배은영;신은주
    • Bulletin of the Korean Chemical Society
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    • v.19 no.1
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    • pp.86-93
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    • 1998
  • Trans-4-(9-anthrylethenyl)-4'-methyl-2,2'-bipyridine(t-aemb) and its bipyridyl Ru complex $[Ru(bpy)_2(t-aemb)](PF_6)_2$ (bpy=2,2'-bipyridine) 1 have been prepared and their excited state properties have been studied. t-Aemb exhibits solvent-dependent fluorescence and efficient trans→cis photoisomerization. 1 shows very weak fluorescence and its photochemically reactive. Fluorescence is wavelength-dependent. While the excitation into the MLCT band makes the complex fluorescent, direct absorption by the t-aemb ligand leads to the photoreaction of t-aemb ligand and no fluorescence is observed. 1 is considered to behave in part as bichromophoric molecule in which $[Ru(bpy)_3](PF_6)_2$ and anthryl group are covalently linked by ethenyl linkage. Because anthryl moiety is not effectively conjugated with bipyridylethenyl moiety due to steric hindrance, weak fluorescence can be explained due to the efficient energy or electron transfer.

Low-Temperature FTIR Spectroscopy of Bacteriorhodopsin and Phoborhodopsin

  • Kandori, Hideki;Furutani, Yuji;Shimono, Kazumi;Iwamoto, Masayuki;Sudo, Yuki;Shichida, Yoshinori;Kamo, Naoki
    • Journal of Photoscience
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    • v.9 no.2
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    • pp.106-109
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    • 2002
  • Archaeal rhodopsins possess retinal molecule as their chromophores, and their light-energy and light-signal conversions are triggered by all-trans to 13-cis isomerization of the retinal chromophore. Relaxation through structural changes of protein then leads to functional processes, proton pump in bacteriorhodopsin (bR) and transducer activation in phoborhodopsin (pR). It is known that sensory rhodopsins can pump protons in the absence of their transducers. Thus, there should be common and specific features in their protein structural changes for function. In this paper, our r ecent studies on pR from Natronobacterium pharaonis (ppR) by means of low-temperature Fourier-transform infrared (FTIR) spectroscopy are compared with those of bR. In particular, protein structural changes upon retinal photoisomerization are studied. Comparative investigation of ppR and bR revealed the similar structures of the polyene chain of the chromophore and water-containing hydrogen-bonding network, whereas the structural changes upon photoisomerization were more extended in ppR than in bR. Extended protein structural changes were clearly shown by the assignment of the C=O stretch of Asnl05. FTIR studies of a ppR mutant with the same retinal binding site as in bR revealed that the Schiff base region is important to determine their colors.

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Photoresponsive Behavior of Liquid-Crystalline Networks

  • Yu, Yanlei;Ikeda, Tomiki;Nakano, Makoto
    • 한국정보디스플레이학회:학술대회논문집
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    • 2002.08a
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    • pp.34-37
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    • 2002
  • Freestanding azobenzene-containing liquidcrystalline network (LCN) films. with macroscopic uniaxial molecular alignment were prepared by insitu photopolymerization. By polarizing microscopy, fiber-like structures aligned in one direction were observed. Furthermore, with a confocal laser scanning microscope (CLSM), it was confirmed that the fiber-like structures were formed even in the bulk of the LCNs. Upon UV light irradiation to cause trans-cis photoisomerization of the azobenzene molecules, the LCNfilms underwent a significant and anisotropic bending toward the irradiation direction of UV light. When the bent LCNfilms were exposed to Vis light, unbending of the LCN films immediately took place and the initial flat LCN films were restored. This bending and unbending behavior of the LCN films could be repeated just by changing the wavelength of the irradiation light. It was suggested that the bending was induced by an absorption gradient which produced a volume difference between the front surface area and the bulk of the network films.

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Photosensitive Polymers: Effects of Photoreactive Group and UV-Exposure on Alignment of Liquid-Crystals on the Film Surface

  • Ree, Moon-Hor;Kim, Sang-Il;Lee, Seung-Woo
    • 한국정보디스플레이학회:학술대회논문집
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    • 2000.01a
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    • pp.41-42
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    • 2000
  • Photosensitive polyimides containing cinnamoyl and coumarin side groups were synthesized in a high molecular weight, giving a good quality of films. Nematic liquid-crystal (LC) molecules on the film were aligned along the direction with an angle of $97-99^{\circ}$ respect to the polarization of ultraviolet (UV) light. The LC alignment was induced mainly by the photoaligned polymer chains made by the first UV-exposure even though the film was treated by multiple exposures with changing the polarization of UV light. From these results, it is concluded that the LC alignment on the film is induced by the photodimerization rather than the trans-cis photoisomerization.

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Dynamic Behavior of Photoinduced Birefringence of Copolymers Containing Aminonitro Azobenzene Chromophore in the Side Chain

  • 최동훈;강석훈
    • Bulletin of the Korean Chemical Society
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    • v.20 no.10
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    • pp.1186-1194
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    • 1999
  • Photoresponsive side chain polymers containing aminonitro azobenzene were synthesized for studying optically induced birefringence. Four different copolymers were prepared using methacrylate, a-methylstyrene, and itaconate monomer. Two copolymers are totally amorphous and the other two are liquid crystalline in nature. Trans-to-cis photoisomerization was observed under the exposure of UV light with UV-VIS absorption spectroscopy. Reorientation of polar azobenzene molecules induced optical anisotropy under a linearly polarized light at 532 nm. The dynamic parameters of optically induced birefringence let us compare the effect of polymeric structure on the rate of growth and decay of the birefringence. Besides the effect of glass transition temperature on the dynamics of photoinduced birefringence, we focused our interests on the geometrical hindrance of polar azobenzene molecules and cooperative motion of environmental mesogenic molecules in the vicinity of polar azobenzene moiety.

Thermotropic Liquid Crystalline and Photochemical Phase Transition Behavior of Octa[8-{4-(4'-cyanophenylazo)phenoxy}]octyl and Octa[8-{4-(4'-cyanophenylazo) phenoxycarbonyl}]heptanoated Disaccharides (옥타[8-{4-(4'-시아노페닐아조)펜옥시}]옥틸 그리고 옥타[8-{4-(4'-시아노페닐아조) 펜옥시카보닐}]헵타노화 이당류의 열방성 액정과 광화학적 상전이 거동)

  • Kim, Hyo Gap;Jung, Seung Yong;Jeong, Hee Sung;Ma, Yung Dae
    • Polymer(Korea)
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    • v.36 no.6
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    • pp.776-788
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    • 2012
  • Octa[8-{4-(4'-cyanophenylazo)phenoxy}]octyl and octa[8-{4-(4'-cyanophenylazo)phenoxycarbonyl}]heptanoated disaccharide derivatives were synthesized by reacting cellobiose, maltose, and lactose with 1-{4-(4'-cyanophenylazo) phenoxy}octylbromide or 1-{4-(4'-cyanophenylazo)phenoxycarbonyl}]heptanoyl chloride, and their thermotropic liquid crystalline and photochemical phase transition behavior were investigated. All the {(cyanophenylazo)phenoxy} octyl disaccharide ethers (CADETs) formed monotropic nematic (N) phases, whereas all the {(cyanophenylazo) phenoxycarbonyl}heptanoated disaccharide esters (CADESs) exhibited enantiotropic N phases. Compared with CADETs, CADESs showed higher isotropic (I)-to-N phase transition temperatures. Photoirradiation of the disaccharide derivatives in a glass cell or in a cell with a rubbed polyimide (PI) alignment layer at a N phase resulted in disappearance of the N phase due to trans-cis photoisomerization of azobenzene, and the initial N phase was recovered when the irradiated sample was kept in the dark because of cis-trans thermal isomerization and reorientation of trans-azobenzenes. The rates of the photochemical N-I and the thermal I-N phase transition of disaccharide derivatives in a cell with a rubbed PI alignment layer were faster than those in a glass cell, and were significantly different from those observed for the monomesogenic compounds containing cyanoazobenzene and the 4-{4'-(cyanophenylazo)phenoxy}octyl glucose and cellulose ethers. The results were discussed in terms of difference in cooperative motion of azobenzene groups due to the flexibility of the main chain, the number of mesogenic units per repeating units, and the distance between the azobenzene groups.

Electrical Properties of 4th generational Dendrimer Containing Azo-group (아조 기능기를 가진 제4세대 덴드리머의 전기적 특성)

  • Yang, Ki-Sung;Ock, Jin-Young;Jung, Sang-Bum;Kim, Chung-Kyun;Park, Jae-Chul;Kwon, Young-Soo
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2003.07b
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    • pp.904-907
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    • 2003
  • We synthesized dendrimers containing light switchable units, azobenzene group. To apply to the molecular level devices or data storage system using Langmuir-Blodgett(LB) film, we firstly investigated the monolayer behavior using the surface pressure-area(${\pi}-A$) isotherms at air-water interface. And then the surface pressure shift of monolayer by light irradiation was also measured to the dendrimer with azobezene group. As a result, the monolayer of dendrimer with azobenzene group showed the reversible photo-switching behavior by the isomerization of azobenzene group in their periphery. This results suggest that the dendrimers with azobenzene group can be applied to high efficient nano-device of molecular level. And we measured the electrical properties by MIM and STM. The dendrimer with azobenzene group compared trans form and cis form at electrical properties.

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Luminescence Studies of N-Methyllutidone, an Unusually High Triplet Energy Sensitizer (N-메틸루티돈의 루미네센스에 관한 연구)

  • Sang Chul Shim;Myung Ho Hyun;Kuy Ho Chae
    • Journal of the Korean Chemical Society
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    • v.22 no.1
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    • pp.45-51
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    • 1978
  • The luminescence of N-methyllutidone is studied in ethanol matrix at $77^{\circ}C$K. No fluorescence is observed but a strong phosphorescence with the quantum yield of 0.1 and the lifetime of 0.2 sec is recorded. An unusually high triplet energy of 85.1 kcal/mole is determined for the compound from the O-O band of phosphorescence. The cis ${\leftrightarrow}$ trans photoisomerization of high triplet energy olefins such as 2-hexene and trans-1,4-dichlorobutene-2 is efficiently sensitized by N-methyllutidone substantiating the high triplet energy of the compound. The negative polarization of O-O band reveals the emitting triplet state to be $({\pi},{\pi}^*)^3$ state. Alkaline metal salts such as lithium chloride enhances the phosphorescence intensity through cation-N-methyllutidone coordination widening the gap between $({\pi},{\pi}^*)^3$and $(n,{\pi}^*)^3$ states.

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