Co-reporter:Tomohiro Ichikawa, Masakazu Morimoto, Masahiro Irie
Dyes and Pigments 2017 Volume 137() pp:214-220
Publication Date(Web):February 2017
DOI:10.1016/j.dyepig.2016.10.010
•A diarylethene having a benzo[b]phosphole P-oxide group underwent a diastereoselective photocyclization reaction.•The diastereomeric excess value changed depending on the photoreaction conversion.•The diarylethene showed a high photocyclizaiton quantum yield.A photochromic diarylethene derivative 1 having a chiral benzo[b]phosphole P-oxide at the aryl moiety underwent a diastereoselective photocyclization reaction in acetonitrile upon irradiation with ultraviolet (UV) light. It was found that the diastereomeric excess (d.e.) value changes depending on the conversion ratio from the open- to closed-ring isomer as well as the irradiation wavelength. This is attributed to the difference in the photocycloreversion quantum yields of diastereomers of the closed-ring isomer. The diarylethene showed a high photocyclization quantum yield owing to a high population of photoreactive conformers of the open-ring isomer by the steric effect of the benzo[b]phosphole P-oxide group.
Co-reporter:Yuta Takagi, Masakazu Morimoto, Ryota Kashihara, Sae Fujinami, Syoji Ito, Hiroshi Miyasaka, Masahiro Irie
Tetrahedron 2017 Volume 73, Issue 33(Issue 33) pp:
Publication Date(Web):17 August 2017
DOI:10.1016/j.tet.2017.03.040
Turn-on mode fluorescence switching molecules are applicable to super-resolution fluorescence microscopy, such as PALM (photoactivation localization microscopy), STORM (stochastic optical reconstruction microscopy) or RESOLFT (reversible saturable (switchable) optical linear fluorescence transitions) microscopy. Here we report on a molecular design strategy to control the cycloreversion quantum yield of the turn-on mode fluorescent diarylethenes, 1,2-bis(2-ethyl-6-aryl-1-benzothiophene-1,1-dioxide-3-yl)perfluorocyclopentenes. Diarylethene derivatives having ortho-substituted phenyl rings at 6- and 6′-positions of 1,2-bis(2-ethyl-1-benzothiophene-1,1-dioxide-3-yl)perfluorocyclopentene were synthesized and their photophysical and photochemical properties were evaluated. The ortho-substitution of the phenyl rings with fluorine or methyl groups decreases the extension of π-conjugation length, resulting in a small blue shift of the absorption spectrum and a substantial increase in the cycloreversion quantum yield from 10−4 to 10−2 without significant influence on the fluorescence quantum yield. Water-soluble derivatives having sodium sulfonate groups were also synthesized. These derivatives fulfill requirements necessary for the application to RESOLFT super-resolution fluorescence microscopy.Download high-res image (150KB)Download full-size image
Co-reporter:Eri Hatano; Dr. Masakazu Morimoto;Dr. Takahito Imai;Dr. Kengo Hyodo;Ayako Fujimoto;Ryo Nishimura;Dr. Akiko Sekine;Dr. Nobuhiro Yasuda; Dr. Satoshi Yokojima;Dr. Shinichiro Nakamura; Dr. Kingo Uchida
Angewandte Chemie International Edition 2017 Volume 56(Issue 41) pp:12576-12580
Publication Date(Web):2017/10/02
DOI:10.1002/anie.201706684
AbstractA diarylethene with a perfluorocyclohexene ring formed hollow crystals by sublimation under normal pressure. Upon UV irradiation of the crystals, they showed remarkable photosalient phenomena and scattered into small pieces. The speed of the flying debris released from the crystal by UV irradiation exceeded several meters per second. To clearly show a photosalient effect resembling the scattering behavior of Impatiens on a smaller scale, small fluorescent beads (1-μm diameter) were inserted into the hollow crystal. Consequently, scattering of the beads was observed as UV irradiation caused deformation and bursting of the hollow structure. This phenomenon is unique to hollow crystals, and the ability to effectively induce remarkable photosalient phenomena is similar to the behavior of hollow-structured Impatiens in nature.
Co-reporter:Tomohiro Ichikawa, Masakazu Morimoto, Hikaru Sotome, Syoji Ito, Hiroshi Miyasaka, Masahiro Irie
Dyes and Pigments 2016 Volume 126() pp:186-193
Publication Date(Web):March 2016
DOI:10.1016/j.dyepig.2015.11.023
•Diarylethenes having benzophosphole and benzothiophene groups were synthesized.•They underwent photochromism and emitted fluorescence in solutions as well as in powder solids.•One of them showed a significant increase of the fluorescence quantum yield in the solid state.Asymmetric diarylethene derivatives having benzophosphole and benzothiophene groups at the aryl moieties were synthesized and their photochromic properties were examined. Three diarylethene derivatives, 1 having benzophosphole and benzothiophene groups, 2 having benzophosphole P-oxide and benzothiophene groups, and 3 having benzophosphole P-oxide and benzothiophene S,S-dioxide groups, were synthesized by appropriately controlled oxidation of benzophosphole and benzothiophene groups. Diarylethenes 1–3 underwent photochromic reactions in acetonitrile as well as in the powder solid state upon alternate irradiation with ultraviolet (UV) and visible light. The closed-ring isomer of diarylethene 3 emitted fluorescence with a quantum yield of 0.05 in acetonitrile solution. The fluorescence quantum yield dramatically increased up to 0.55 in the solid state.
Co-reporter:Eri Hatano;Dr. Masakazu Morimoto;Dr. Kengo Hyodo;Dr. Nobuhiro Yasuda;Dr. Satoshi Yokojima;Dr. Shinichiro Nakamura;Dr. Kingo Uchida
Chemistry - A European Journal 2016 Volume 22( Issue 36) pp:12680-12683
Publication Date(Web):
DOI:10.1002/chem.201603020
Abstract
Crystals of a diarylethene with a perfluorocyclohexene ring exhibit a remarkable photosalient effect upon UV light irradiation that is attributed to the structural changes that occur when going from open- to closed-ring isomers in the crystalline state, together with the existence of two conformers with different photoconversions compared with those of a perfluorocyclopentene derivative. Our current results give a design principle for molecular structures so as to achieve the photosalient effect for photochromic crystals.
Co-reporter:Yuichiro Shoji;Akira Yagi;Masahiro Horiuchi;Masahiro Irie
Israel Journal of Chemistry 2013 Volume 53( Issue 5) pp:303-311
Publication Date(Web):
DOI:10.1002/ijch.201300018
Abstract
Photochromic diarylethene derivatives bearing hydrophilic N,N-bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl)sulfonamide (SO2NTEG2) (1–3) or myo-inositol (4–6) substituents were synthesized. Although the solubility in aqueous solution of the derivatives containing the four tri(ethylene glycol) chains was relatively poor, the solubility was improved by introducing two myo-inositol residues. The derivatives could be dissolved even in pure water and underwent photochromism upon alternate irradiation with ultraviolet (UV) and visible light, in both organic and aqueous solutions. The absorption maxima of the open- and closed-ring isomers of these derivatives and the photostationary conversion ratios from the open- to the closed-ring isomers upon UV irradiation did not change much, even when the solvent polarity was changed. These results indicate that the diarylethene derivatives are mono-molecularly dissolved in aqueous solution and that intermolecular interactions between the derivatives are negligible when the concentration is less than 1×10−4 mol⋅L−1.
Co-reporter:Masakazu Morimoto, Kimie Murata and Tsuyoshi Michinobu
Chemical Communications 2011 vol. 47(Issue 35) pp:9819-9821
Publication Date(Web):28 Jul 2011
DOI:10.1039/C1CC13476K
The electron density of an alkyne moiety is enhanced by the photochromic ring closure of a diarylethene derivative, which allows the thermal addition reaction with a small π-acceptor, tetracyanoethylene, at room temperature.
Co-reporter:Masakazu Morimoto and Masahiro Irie
Chemical Communications 2011 vol. 47(Issue 14) pp:4186-4188
Publication Date(Web):25 Feb 2011
DOI:10.1039/C0CC05729K
The photochromic reaction of a diarylethene derivative having imidazoline rings reversibly modulates the dielectric properties of the crystal, which is based on the intermolecular proton transfer in one-dimensional (1D) hydrogen-bonded chains.
Co-reporter:Masakazu Morimoto, Masahiro Irie
Tetrahedron Letters 2009 50(26) pp: 3404-3407
Publication Date(Web):
DOI:10.1016/j.tetlet.2009.02.139
Co-reporter:Masakazu Morimoto, Seiya Kobatake and Masahiro Irie
Chemical Communications 2008 (Issue 3) pp:335-337
Publication Date(Web):25 Oct 2007
DOI:10.1039/B713694C
A photochromic diarylethene containing naphthyl groups formed a chiral crystal when co-crystallized with octafluoronaphthalene, although both molecules are achiral, and underwent highly enantioselective photocyclization owing to the conformational confinement in the crystal.
Co-reporter:Masakazu Morimoto and Masahiro Irie
Chemical Communications 2011 - vol. 47(Issue 14) pp:NaN4188-4188
Publication Date(Web):2011/02/25
DOI:10.1039/C0CC05729K
The photochromic reaction of a diarylethene derivative having imidazoline rings reversibly modulates the dielectric properties of the crystal, which is based on the intermolecular proton transfer in one-dimensional (1D) hydrogen-bonded chains.
Co-reporter:Masakazu Morimoto, Seiya Kobatake and Masahiro Irie
Chemical Communications 2008(Issue 3) pp:NaN337-337
Publication Date(Web):2007/10/25
DOI:10.1039/B713694C
A photochromic diarylethene containing naphthyl groups formed a chiral crystal when co-crystallized with octafluoronaphthalene, although both molecules are achiral, and underwent highly enantioselective photocyclization owing to the conformational confinement in the crystal.
Co-reporter:Masakazu Morimoto, Kimie Murata and Tsuyoshi Michinobu
Chemical Communications 2011 - vol. 47(Issue 35) pp:NaN9821-9821
Publication Date(Web):2011/07/28
DOI:10.1039/C1CC13476K
The electron density of an alkyne moiety is enhanced by the photochromic ring closure of a diarylethene derivative, which allows the thermal addition reaction with a small π-acceptor, tetracyanoethylene, at room temperature.