Unprecedented Stability of a Photochromic Bisthienylethene Based on Benzobisthiadiazole as an Ethene Bridge

Zhu, Weihong; Yang, Yuhao; Métivier, Rémi; Zhang, Qiong; Guillot, Régis; Xie, Yongshu; Tian, He; Nakatani, Keitaro

doi:10.1002/ange.201105136

Cited by 21 publications

(12 citation statements)

References 39 publications

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“…The fundamental of the photochromism of diarylethenes is reversible photo-induced ring-opening and ring-closing isomerization. The substitution effects on the absorption spectra and quantum yields have been extensively investigated, which provides detailed information and guidance for designing novel photoswitches with properties desired [18]. Hence, photochromic diarylethenes compounds are the most promising candidates as photoresponsive molecular building blocks to assemble photoresponsive supramolecular systems.…”

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confidence: 99%

Recent advance of photochromic diarylethenes-containing supramolecular systems

Xiao

Zhao

Zhou

et al. 2015

Chinese Chemical Letters

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confidence: 99%

Recent advance of photochromic diarylethenes-containing supramolecular systems

Xiao

Zhao

Zhou

et al. 2015

Chinese Chemical Letters

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“…5-(4-Methoxyphenyl)-2-methylthiophen-3-ylboronic acid was prepared by the reported procedure [11] and was used as a building block to synthesize the desired target molecules. The key intermediates of 4bromo-N-butyl-3-iodo-1,8-naphthalimide, [11] 4,5-dibromo-2,1,3-benzothiadiazole, [12] and 4,5-dibromobenzo [1,2-c:3,4c']bisA C H T U N G T R E N N U N G [1,2,5]thiadiazole [8] were conveniently synthesized from 4-bromo-1,8-naphthalic anhydride, 4-bromobenzene-1,2-di-A C H T U N G T R E N N U N G amine, and benzothiadiazole, [13] respectively. The Suzuki coupling between 4-bromo-N-butyl-3-iodo-1,8-naphthalimide, 4,5-dibromo-2,1,3-benzothiadiazole, 4,5-dibromobenzo [1,2-c:3,4-c']bisA C H T U N G T R E N N U N G [1,2,5]thiadiazole, and 5-(4-methoxyphenyl)-2-methylthiophen-3-ylboronic acid in the presence of a [PdA C H T U N G T R E N N U N G (PPh 3 ) 4 ] catalyst in a mixture of aqueous Na 2 CO 3 (2 m) and 1,4-dioxane under reflux conditions gave the target molecules of BTE-NA, BTA, and BTTA, which were fully characterized by 1 H and 13 C NMR spectroscopy as well as highresolution MS (HRMS; shown in the Experimental Section and the Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

“…In contrast, the previously reported BTTE without methoxy groups adopts an antiparallel conformation on account of the lack of widespread occurrence of intermolecular interactions. [8] Clearly, the methoxy group plays an important role in these crystals due to the presence of the electron-rich O atoms. Moreover, BTTA forms a twin crystal.…”

Section: Resultsmentioning

confidence: 99%

“…The fluorescence quantum yields were measured by the comparison of BTE-NA, BTA, and BTTA with standard 0.05 m quinine sulphate in sulfuric acid. 4-Bromo-N-butyl-3-iodo-1,8-naphthalimide, [11] 4,5-dibromo-2,1,3-benzothiadiazole, [12] 4,5-dibromobenzo [1,2-c:3,4-c']bis-A C H T U N G T R E N N U N G [1,2,5]thiadiazole, [8] and 5-(4-methoxyphenyl)-2-methylthiophen-3-ylboronic acid were prepared according to the established method. [12] All other reagents were of analytical purity and used without further treatment.…”

Section: Methodsmentioning

confidence: 99%

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Aromaticity‐Controlled Thermal Stability of Photochromic Systems Based on a Six‐Membered Ring as Ethene Bridges: Photochemical and Kinetic Studies

Yang

Xie

Zhang

et al. 2012

Chemistry A European J

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Three photochromic compounds--2-butyl-5,6-bis[5-(4-methoxyphenyl)-2-methylthiophen-3-yl]-1 H-benzo[de]isoquinoline-1,3(2 H)-dione (BTE-NA), 4,5-bis[5-(4-methoxyphenyl)-2-methylthiophen-3-yl]benzo[c][1,2,5]thiadiazole (BTA), and BTTA, which contain naphthalimide, benzothiadiazole, and benzobisthiadiazole as six-membered ethene bridges with different aromaticities--were systematically studied in solution, sol-gel, and single-crystal states. They exhibit typical photochromic performance with considerably high cyclization quantum yields. BTE-NA, BTA, and BTTA form a typical donor-π-acceptor (D-π-A) system with significant intramolecular charge transfer (ICT) between HOMO and LUMO upon excitation, thus realizing the fluorescence modulation by both photochromism and solvatochromism. The three ethene bridges with different degrees of aromaticity can provide a systematic comparison of the thermal stability evolution for their corresponding closed forms (c-BTE-NA, c-BTA, and c-BTTA). c-BTE-NA shows first-order decay in various solvents from cyclohexane to acetonitrile. c-BTA only shows first-order decay in polar solvents such as chloroform, whereas it is stable in nonpolar solvents like toluene. In contrast, the less aromatic property of BTTA gives rise to its unprecedented thermal stability in various solvents even at elevated temperatures in toluene (328 K). Moreover, the small energy barrier between the parallel and antiparallel conformers allows the full conversion from BTTA to c-BTTA. In well-ordered crystal states, all three compounds adopt a parallel conformation. Interestingly, BTTA forms a twin crystal of asymmetric nature with interactions between the electron-rich oxygen atom of the methoxy group and the carbon atom of the electron-deficient benzobisthiadiazole moiety. This work contributes to the understanding of aromaticity-controlled thermal stability of photochromic systems based on a six-membered ring as an ethene bridge, and a broadening of the novel building blocks for photochromic bisthienylethene systems.

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“…However, concomitantly, it induces a high aromaticity, thus leading to T-type systems, unless EWG such as benzobisthiadiazoles are introduced [98]. cases, a weaker C-C bond means a higher energy difference between B and A, thus leading to a lower energy barrier to the thermal back-reaction.…”

Section: Influence Of Ethenic Bridge On the Thermal Stability Of The mentioning

confidence: 99%