- Photochromism of diarylethenes having nitronyl nitroxides
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The photoreactivities of photochromic diarylethenes having nitronyl nitroxide radicals were studied in terms of the measurement of the quantum yields and the conversions in the photostationary state. (C) 2000 Elsevier Science Ltd.
- Matsuda, Kenji,Irie, Masahiro
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- A prominent bathochromic shift effect of indole-containing diarylethene derivatives
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The potential implication of photochromic materials with absorption and reactivity in the near-infrared region is far-reaching. In this work, three novel bisindole-containing diarylethene derivatives 1o-3o have been successfully synthesized and their photochromic behaviour exhibits a strong bathochromic shift effect compared with bisbenzothiophene diarylethene 4o. These new bisindole-diarylethene compounds 1o-3o are highly sensitive to photo-stimuli both in solution and in poly(methyl methacrylate) films. Besides, 1o-3o exhibit an excellent reversible fluorescence switching behavior modulated by optical stimuli. This journal is
- Cheng, Hong-Bo,Huang, Yao-Dong,Zhao, Lina,Li, Xu,Wu, Hai-Chen
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- Photochromic properties of diarylethene derivatives having chryso[b]thiophene rings
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Diarylethene derivatives having one or two chryso[b]thiophene ring(s) have been synthesized. In solution the derivatives underwent photochromism and the derivative with one chryso[b]thiophene ring exhibited photochromism even in the single crystalline pha
- Yamaguchi, Tadatsugu,Fujita, Yuji,Nakazumi, Hiroyuki,Kobatake, Seiya,Irie, Masahiro
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- Ring opening/closure reactions of novel diheteroarylethenes derivatives. Solvent effects
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Three novel diarylethenes derived from benzothiophene were synthesized and their photochemical optical properties studied in four solvents (n-hexane, toluene, acetonitrile and methanol). It was determined that these compounds dramatically increase the light absorption in the visible region upon exposure to UV light, showing two absorption maxima at 420nm and 520nm, respectively. The observed change is completely reverted upon exposure to visible light. The three compounds demonstrate negligible fatigue, excellent stability in the four solvents, and absence of photodegradation and thermal back reactions. This paper also describes a complete study of solvent effects on the kinetics of the ring opening and cycloreversion. While, the UV spectra are little sensitive both to the substitution pattern and to the solvent influence, the kinetics of ring opening/cycloreversion reactions exhibit a more interesting behavior that differs from other diarylethenes reported in the literature. The cyclization kinetics shows a complex order, well fitted by an exponential equation, while the cycloreversion presents first-order kinetics. The whole complex reaction scheme can be explained by the unusual presence of two conformers of the open form, a parallel and an antiparallel conformation. Though other alternative mechanism could explain the kinetics, additional evidence is consistent with the conformational equilibrium proposed: i.e. the solvent influence on the kinetics of the nitrosubstituted substrate, and the double signals for the methyl protons and for the methoxy protons (when present) observed in the nuclear magnetic resonance spectra. These observations are relevant in relation to the application of these novel diarylethenes as potential optical materials. Copyright
- Vazquez, Alvaro J.,Nudelman, Norma Sbarbati
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- Photochromism of diarylethene derivatives having an indene unit
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Photochromic indene derivatives, 1-(2-methyl-1-inden-3-yl)-2-(2-methyl-1- benzothien-3-yl)perfluorocyclopentene and 1-(2-methyl-1-inden-3-yl)-2-(2-methyl- 1-benzofuran-3-yl)perfluorocyclopentene, were synthesized and their photochromic performance was examined.
- Yamaguchi, Tadatsugu,Irie, Masahiro
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- Thermally Irreversible Photochromic Systems. Reversible Photocyclization of 1,2-Bis(2-methylbenzothiophen-3-yl)perfluorocycloalkene Derivatives
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1,2-Bis(2-methylbenzothiophen-3-yl)perfluorocyclopentenes undergo thermally irreversible photochromic reactions in which colouration/decolouration cycles can be repeated more than 104 times without significant loss of performance.
- Hanazawa, Makoto,Sumiya, Ritsuo,Horikawa, Yukio,Irie, Masahiro
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- Optical Communication among Oscillatory Reactions and Photo-Excitable Systems: UV and Visible Radiation Can Synchronize Artificial Neuron Models
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Neuromorphic engineering promises to have a revolutionary impact in our societies. A strategy to develop artificial neurons (ANs) is to use oscillatory and excitable chemical systems. Herein, we use UV and visible radiation as both excitatory and inhibitory signals for the communication among oscillatory reactions, such as the Belousov–Zhabotinsky and the chemiluminescent Orban transformations, and photo-excitable photochromic and fluorescent species. We present the experimental results and the simulations regarding pairs of ANs communicating by either one or two optical signals, and triads of ANs arranged in both feed-forward and recurrent networks. We find that the ANs, powered chemically and/or by the energy of electromagnetic radiation, can give rise to the emergent properties of in-phase, out-of-phase, anti-phase synchronizations and phase-locking, dynamically mimicking the communication among real neurons.
- Gentili, Pier Luigi,Giubila, Maria Sole,Germani, Raimondo,Romani, Aldo,Nicoziani, Andrea,Spalletti, Anna,Heron, B. Mark
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- A diarylethene with two nitronyl nitroxides: Photoswitching of intramolecular magnetic interaction
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A diarylethene having two nitronyl nitroxides, 1,2-bis[6-(1-oxyl-3-oxide-4,4,5,5-tetramethylimidazolin- 2-yl)-2-methyl-1-benzothiophen-3-yl]hexafluorocyclopentene (2a), was synthesized in an attempt to control the intramolecular magnetic interaction by photoirradiation. The photochemical conversions from open-ring isomer 2a to closed-ring isomer 2b and from 2b to 2a were both almost 100%. Magnetic measurement revealed the antiferromagnetic interaction between two nitronyl nitroxides remarkably increased from 2J/k(B) = -2.2 K to 2J/k(B) = -11.6 K when the diarylethene spin coupler was switched from the open-ring isomer 2a to the closed-ring isomer 2b. ESR measurements were also carried out for both 2a and 2b in benzene solutions at room temperature and in MTHF solid solutions at cryogenic temperature. Both ESR and magnetic measurement indicated that the intramolecular interaction was switched by the photochromic spin coupler.
- Matsuda, Kenji,Irie, Masahiro
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- Reversible photoswitching of triplet-triplet annihilation upconversion using dithienylethene photochromic switches
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Reversible photoswitched triplet-triplet annihilation upconversion (TTA UC) was demonstrated with dithienylethene (DTE) derivatives as the photochromic units, 2,6-diiodoBodipy as the triplet photosensitizer, and perylene as the triplet acceptor/emitter. T
- Cui, Xiaoneng,Zhao, Jianzhang,Zhou, Yuhan,Ma, Jie,Zhao, Yilong
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- Photochromism of diarylethene derivatives having n-alkylbenzothiophene and n-alkylbenzofuran units
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Photochromic diarylethenes having benzofuran and benzothiophene rings have been synthesized and their photochromic performance in a single-crystalline phase has been examined. Although 1,2-bis(2-methyl-1-benzothiophen-3-yl) perfluorocyclopentene (1a) is photochemically inactive in the single-crystalline phase, diarylethene derivatives having a benzofuran ring (2a and 3a) undergo photochromism in the single-crystalline phase. 1-(1-Benzofuran-3-yl)-2-(1- benzothiophen-3-yl)hexafluorocyclopentene having ethyl, propyl, and butyl chains at the 2-position (4a-6a) were also synthesized. The derivative having propyl chains (5a) underwent photochromism in a single-crystalline phase. Upon UV irradiation, the crystal showed a brilliant red color in the single-crystalline phase.
- Yamaguchi, Tadatsugu,Irie, Masahiro
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- Photochromism of diarylethenes on porous aluminum oxide: Fatigue resistance and redox potentials of the photochromes
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The photochromism of three diarylethene derivatives was examined on porous aluminum oxide. Upon alternate irradiation with UV and visible light, the diarylethenes having thiophene rings decomposed easily, while a derivative having benzothiophene rings underwent a reversible photochromic reaction. The decomposition started from the closed-ring isomers of the dithienylethenes. The decomposition mechanism was discussed based on the oxidation potentials of the compounds.
- Uchida, Kingo,Fujita, Masayuki,Aoi, Yoshifumi,Saito, Mitsunori,Irie, Masahiro
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- Photochromism of bis(2-alkyl-1-benzofuran-3-yl)perfluorocyclopentene derivatives
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Photochromic diarylethene derivatives having benzofuran heteroaryl groups, bis(2-methyl-1-benzofuran-3-yl)perfluorocyclopentene and bis(2-butyl-1- benzofuran-3-yl)perfluorocyclopentene, were synthesized, and their photochromic performance was examined in hexane solution as well as in the single-crystalline phase. The compounds exhibited photochromic reactivity even in the single-crystalline phase.
- Yamaguchi, Tadatsugu,Irie, Masahiro
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- Fluorescence property of photochromic diarylethenes with indole groups
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Diarylethenes having a fluorescent indole ring as the aryl group 1a and 2a were synthesized. Upon alternate irradiation with 366 nm and visible (λ > 480 nm) light, 1a underwent reversible photocyclization reactions to produce closed-ring isomer 1b. The fluorescence intensity also reversibly changed along with the reactions. The fluorescence quantum yields of the open-ring isomers 1a and 2a were 4.6 and 6.3% respectively, while the yields of the closed-ring isomers 1b and 2b were almost zero. The fluorescence quantum yields decreased with the increase in the photocyclization quantum yields.
- Yagi, Kyoko,Irie, Masahiro
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- Photoirradiation wavelength dependence of cycloreversion quantum yields of diarylethenes
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The cycloreversion quantum yields of compounds 1b and 2b increased upon irradiation with light at shorter wavelengths. The irradiation wavelength dependence is ascribed to the energy barrier on the 2A potential energy surface in the excited electronic state.
- Sumi, Takaki,Takagi, Yuta,Yagi, Akira,Morimoto, Masakazu,Irie, Masahiro
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- Photochromic properties of diarylethene derivatives having benzofuran and benzothiophene rings based on regioisomers
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Photochromic diarylethene regioisomers having benzothiophene and benzofuran rings were synthesized and their structures were confirmed by X-ray crystallography. The photochromic properties of these diarylethenes were examined in solution as well as in the single-crystalline phase. We found that a diarylethene having 3-methylbenzofuran (FR2) ring show photochromism upon irradiation with UV light. For bis(3-methylbenzofuran) (BFR2) derivatives, the absorption band of the closed-ring isomer was longer than that of the open-ring isomer. The closed-ring isomer of the diarylethene derivatives having one 2-methylbenzofuran (FR3) ring showed a high absorption coefficient (more than 104 dm3mol-l: cm-1). Although the distance between two reactive carbon atoms was within 0.42 nm, some diarylethene derivatives showed no photochromic reactions in the single-crystalline phase. Diarylethene derivatives having one 2-methylbenzofuran (FR3) ring efficiently showed photochromism in the single-crystalline phase.
- Yamaguchi, Tadatsugu,Uehida, Kingo,Irie, Masahiro
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- Effect of imino nitroxyl and nitronyl nitroxyl groups on the photochromic reactivity of diarylethenes
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(Chemical Equation Presented) Diarylethene derivatives having imino nitroxide and nitronyl nitroxide have been prepared to examine the effect of the radical substituents on the photochromic reactivity of 1,2-bis(2-methyl-1- benzothiophen-3-yl)perfluorocyclopentene. These radical substituents reduce the quantum yields of both cyclization and cycloreversion reactions. The nitronyl nitroxyl moiety is more effective to suppress the reactivity in comparison with the imino nitroxide moiety.
- Tanifuji, Naoki,Matsuda, Kenji,Irie, Masahiro
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- Photokinetics of two novel photochromic diarylethenes derived from benzothiophene
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Two new unsymmetrically substituted photochromic diarylethenes, namely 3-[3, 3,4,4,5,5-hexafluoro-2-(2-methylbenzothien-3-yl)cyclopent-1-en-1-yl]-2- methyl-6-methoxy-1- benzothiophene and 3-[3,3,4,4,5,5-hexafluoro-2-(2- methylbenzothien-3-yl)cyclopent-1-en-1-yl]-2-methyl-6-methoxy-7-nitro-1- benzothiophene, were synthesized. Their optical properties and kinetics of cyclization and cycloreversion were determined in four solvents and compared with the symmetrical diarylethene (3,3,4,4,5,5-hexafluorocyclopent-1-en-1,2- diyl)bis(2-methyl-1-benzothiophene). While the UV spectra of the three compounds are almost insensitive to solvent changes, the rates of the ring-opening and ring-closure reactions exhibit interesting kinetic behavior that differs from other diarylethenes reported in the literature. The cycloreversion for the three compounds follows first-order kinetics, whereas the cyclization cannot be described by a simple kinetic law. Different approaches were tested, and a complex exponential equation could be derived that fits the experimental data. The unusual presence of two ring-opened conformational isomers, one of them nonphotochromic, is proposed for the ring-opened compounds to explain the derived kinetic law and observed solvent effects. These results are of interest in relation to the application of the novel diarylethenes as potential optical materials.
- Vazquez, A.,Nudelman, N. Sbarbati
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- Correlating Reaction Dynamics and Size Change during the Photomechanical Transformation of 9-Methylanthracene Single Crystals
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Photomechanical molecular crystals that expand under illumination could potentially be used as photon-powered actuators. In this study, we find that the use of high-quality single crystals of 9-methylanthracene (9MA) leads to more homogeneous reaction kinetics than that previously seen for polycrystalline samples, presumably due to a lower concentration of defects. Furthermore, simultaneous observation of absorbance and shape changes in single crystals revealed that the dimensional change mirrors the reaction progress, resulting in a smooth expansion of 7 % along the c-axis that is linearly correlated with reaction progress. The same expansion dynamics are highly reproducible across different single crystal samples. Organic single crystals exhibit well-defined linear expansions during 100 % photoconversion, suggesting that this class of solid-state phase change material could be used for actuation.
- Bardeen, Christopher J.,Chalek, Kevin,Kitagawa, Daichi,Kobatake, Seiya,Morimoto, Kohei,Mueller, Leonard J.,Tong, Fei
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supporting information
(2021/12/09)
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- Diastereoselective self-assembly of a triple-stranded europium helicate with light modulated chiroptical properties
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Chiroptical photoswitches are of increasing interest for their potential in advanced information technologies. Herein, an achiral bis-β-diketonate ligand (o-L) with a photoresponsive diarylethene moiety as a linker was designed, which co-assembled with Eu3+ions andR- andS-bis(diphenylphosphoryl)-1,10-binaphthyl (R/S-BINAPO) as chiral ancillaries to form dinuclear triple-stranded helicates, [Eu2(o-L)3(R/S-BINAPO)2]. The helicates in the enantiopure form were confirmed by1H,19F,31P NMR and DOSY NMR analyses. Furthermore, the mirror-image CD and CPL spectra also demonstrate the existence of stable ground- and excited-state chiralities in solution. When exposed to alternate ultraviolet and visible light, the helicates showed reversible color variations from colorless to purple, followed by the presence of light-triggered quadruple optical and chiroptical outputs, named CD, PL, CPL andglumswitches. With these light-modulated optical outputs, the possibility for the fabrication of IMPLICATION and INHIBIT logic gates was discussed.
- Zhang, Zhihui,Zhou, Yanyan,Gao, Ting,Yan, Pengfei,Zou, Xiaoyan,Li, Hongfeng
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p. 4604 - 4612
(2021/04/12)
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- Metal-directed synthesis of quadruple-stranded helical Eu(iii) molecular switch: A significant improvement in photocyclization quantum yield
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The self-assembly of a quadruple-stranded Eu(iii) helicate induces the conformation transformation of a DAE-based photochromic ligand from parallel to antiparallel, which brings a significant improvement in the photocyclization quantum yield (Φo-c) as compared with the free ligand. Furthermore, the photocontrolled open- and closed-rings of the ligand realized a reversible modulation toward Eu3+ center emission.
- Gao, Ting,Li, Hongfeng,Yan, Pengfei,Zhang, Yuan,Zhou, Yanyan
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supporting information
p. 13213 - 13216
(2020/11/09)
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- Photoswitchable Turn-on Mode Fluorescent Diarylethenes: Strategies for Controlling the Switching Response
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A new type of photoswitchable fluorescent diarylethenes, which have no fluorophore unit but emit strong fluorescence (ˉf3 0.9) in the closed-ring isomers, has been developed. They are sulfone derivatives of 1,2-bis(2-alkyl-4-methyl-5-phenyl-3-thienyl)perfluorocyclopentenes and 1,2-bis(2-alkyl-1-benzothiophen-3-yl)perfluorocyclopentenes. By chemical modifications of the structures their switching response was tuned to meet the requirements for super-resolution fluorescence microscopies. The water-soluble derivatives have been successfully applied to acquire super-resolution bioimages using a single-wavelength visible beam.
- Irie, Masahiro,Morimoto, Masakazu
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p. 237 - 250
(2018/02/21)
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- Thieme Chemistry Journal Awardees - Where are They Now? The Influence of Electron-Withdrawing Groups at the 2- and 2′-Positions of Dibenzothienylethenes on Molecular Switching
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Three dibenzothienylethenes that carry a methyl, a trifluoromethyl, or a fluoro substituent in the 2- and 2′-position were synthesised in short multistep syntheses, respectively. The trifluoromethyl and fluoromethyl substituents significantly improve the absorption properties of the corresponding open and closed isomers (both in the UV-A and in the visible range). The increasing electron deficiency (i) enlarges the portion of the closed and coloured diarylethene isomer in the corresponding photostationary states and slows down the closing and opening isomerisation, (ii) the switching reactions, both closing and opening, are slowed down, and (iii) the switching quantum yields are lowered.
- Hofs?β, Robert,Rombach, David,Wagenknecht, Hans-Achim
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p. 1422 - 1426
(2017/07/22)
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- Photomobile polymer materials: Photoresponsive behavior of cross-linked liquid-crystalline polymers with mesomorphic diarylethenes
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Cross-linked liquid-crystalline (LC) polymers with a mesomorphic diarylethene were prepared to demonstrate a versatile strategy for cross-linked photochromic LC polymers as photomobile materials. Upon exposure to UV light to cause photocyclization of the diarylethene chromophore, the cross-linked polymer films bend toward an actinic light source. By irradiation with visible light to cause a closed-ring to open-ring isomerization, the bent films revert to the initial flat state. Without visible-light irradiation, the bent films remain bent even at 120 8C, indicating high thermal stability of the cross-linked diarylethene LC polymers.
- Mamiya, Jun-Ichi,Kuriyama, Akito,Yokota, Naoki,Yamada, Munenori,Ikeda, Tomiki
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p. 3174 - 3177
(2015/03/05)
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- A luminescent steroid-based organogel: ON-OFF photoswitching by dopant interplay and templated synthesis of fluorescent nanoparticles
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The modulation of the fluorescence emission of a perylene dye between ON and OFF states was achieved with high efficiency by means of a diarylethene photochromic compound in an organogel medium. Fluorescent gels were prepared from a steroidal low molecular weight organogelator doped with the perylene fluorophore. The compatibility of the photochromic compound in this medium and the non-destructive readout capability were demonstrated. The dye doped organogel was further used as a template and an innovative method was employed to grow fluorescent silica spherical nanoparticles with physically and chemically admixed perylene dye.
- Edelsztein, Valeria C.,Jares-Erijman, Elizabeth A.,Spagnuolo, Carla C.,Di Chenna, Pablo H.,Muellen, Klaus
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supporting information
p. 21857 - 21861,5
(2020/09/02)
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- A convenient method for the preparation of mono- and bis-substituted photochromic bis(benzothienyl)perfluorocyclopentenes via regioselective Friedel-Crafts acylation
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The regioselective Friedel-Crafts acylation of 1,2-bis(2-methylbenzo[b] thien-3-yl)hexafluorocyclopentene was developed. Depending on the reaction conditions, mono- or bis(bromoacetyl) derivatives are formed as single products in good yields. Further heterocyclizations involving α-bromoketone moieties gave a series of new photochromic compounds.
- Bogacheva, A. M.,Charushin, V. N.,Yarovenko, V. N.,Struchkova, M. I.,Krayushkin, M. M.,Levchenko, K. S.,Shmelin, P. S.,Kobeleva, O. I.,Valova, T. M.,Barachevsky, V. A.
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p. 5948 - 5951,4
(2020/08/20)
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- Practical synthesis of photochromic diarylethenes in integrated flow microreactor systems
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An effective method for the synthesis of photochromic diarylethenes through the generation of heteroaryllithiums and subsequent reaction with octafluorocyclopentene has been developed by using integrated flow microreactor systems. Reactions can be conducted without using cryogenic conditions by virtue of effective temperature and residence time control, although much lower temperatures (-1. Therefore, the present integrated flow microreactor method serves as a practical way of synthesizing various photochromic diarylethene derivatives. Too successful to be cool: An effective method for the synthesis of photochromic diarylethenes has been developed by using integrated flow microreactor systems. Reactions can be conducted without the need for cryogenic conditions by using these systems (see picture). The synthesis of unsymmetrical diarylethenes, which is difficult to achieve by using conventional macro batch systems, has also been accomplished. Copyright
- Asai, Tatsuro,Takata, Atsushi,Nagaki, Aiichiro,Yoshida, Jun-Ichi
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experimental part
p. 339 - 350
(2012/06/30)
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- Photon-quantitative reaction of a dithiazolylarylene in solution
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Ready for action: An excellent quantum yield was observed for a photocoloration reaction of a photochromic molecule based on a triangular terarylene structure. The molecule is brought into a conformation favorable for photocyclization by multiple intramolecular interactions, including CHi-N hydrogen bonding and Si-N and CHi-π interactions (see picture).
- Fukumoto, Sayo,Nakashima, Takuya,Kawai, Tsuyoshi
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supporting information; experimental part
p. 1565 - 1568
(2011/04/15)
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- A perfluorocyclopentene based diarylethene bearing two terpyridine moieties - Synthesis, photochemical properties and influence of transition metal ions
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The synthesis of a perfluorocyclopentene based diarylethene bearing two terpyridine units is reported. Furthermore studies of the free ligand's photochromism and investigations regarding the influence of various transition metal ions on the photochromic reaction are presented. The photochromism of the central diarylethene unit is strongly dependent on the transition metal present, vice versa the photochromic reaction seems to influence the MLCT transition of a binuclear Ru(II) complex.
- Mattay, Jochen,Wehmeier, Falk
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scheme or table
(2010/08/20)
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- Synthesis of photochromic diarylethenes using a microflow system
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An effective method for the synthesis of photochromic diarylethenes based on microflow systems has been developed, and the synthesis of unsymmetrical diarylethenes which is difficult to achieve using conventional macro batch systems, has been accomplished. The Royal Society of Chemistry.
- Ushiogi, Yousuke,Hase, Tomoyuki,Iinuma, Yoshiharu,Takata, Atsushi,Yoshida, Jun-Ichi
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p. 2947 - 2949
(2008/02/10)
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- Control of cycloreversion quantum yields of diarylethenes by introduction of substituants at the reactive carbons
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Several diarylethene derivatives having various substituents at the reactive carbons were prepared and the quantum yields were measured. Although the cyclization quantum yields were scarcely affected by the introduction of substituents, the cycloreversion quantum yields varied depending on the substituents.
- Morimitsu, Kentaro,Kobatake, Seiya,Irie, Masahiro
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p. 151/[451]-154/[454]
(2007/10/03)
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- Photochromic reactions of diarylethenes with isopropyl groups
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Photochromic bisbenzothienylethene has two conformers, photo-reactive anti-parallel and inactive parallel ones. The cyclization quantum yield is dependent on the ratio of the two conformers. By the introduction of bulky substituents at 2-positions of the benzothiophene rings, the cyclization quantum yield increased along with the increase in the ratio of the anti-parallel conformer.
- Uchida, Kingo,Tsuchida, Eriko,Nakamura, Sinichiro,Kobatake, Seiya,Irie, Masahiro
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p. 333/9 - 338/14
(2007/10/03)
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