Photo- and ionochromic N-acylated 2-(aminomethylene)benzo[b]thiophene-3(2H)-ones containing a terpyridine receptor

New photo- and ionochromic N-acylated 2-(aminomethylene)benzo[b]thiophen-3(2H)-ones containing a terpyridine receptor have been synthesized. They absorb in the visible region of the spectrum at 423–426 nm and exhibit emission at 463–468 nm. Their irradiation in acetonitrile with light of 436 nm lead...

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Главные авторы:	Demidov, O. P., Демидов, О. П.
Формат:	Статья
Язык:	English
Опубликовано:	Elsevier B.V. 2025
Темы:	Fluorescence Photochromism N → O acyl rearrangement Molecular switches
Online-ссылка:	https://dspace.ncfu.ru/handle/123456789/29631
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spelling	ir-123456789-296312025-02-06T07:52:42Z Photo- and ionochromic N-acylated 2-(aminomethylene)benzo[b]thiophene-3(2H)-ones containing a terpyridine receptor Demidov, O. P. Демидов, О. П. Fluorescence Photochromism N → O acyl rearrangement Molecular switches New photo- and ionochromic N-acylated 2-(aminomethylene)benzo[b]thiophen-3(2H)-ones containing a terpyridine receptor have been synthesized. They absorb in the visible region of the spectrum at 423–426 nm and exhibit emission at 463–468 nm. Their irradiation in acetonitrile with light of 436 nm leads to a multi-stage rearrangement, including Z/E isomerization about the C[dbnd]C bond, N → O migration of the acyl group and the formation of non-emissive O-acylated E-isomers, which were isolated preparatively. Their structure was established unambiguously by IR, 1H, 13C NMR spectroscopy and HR mass spectrometry. The reverse thermal reaction with O → N migration of the acyl group is catalyzed by acid catalysts. N-Acylated compounds in acetonitrile selectively form non-fluorescent complexes with Fe2+ cations, which is accompanied by the naked-eye effect with changing the color from yellow to maroon. A successful selective interaction with AcO− led to the restoration of the initial absorption and emission properties. Density functional theory (DFT) calculations at the M06-2X/def2-TZVP level with the PCM solvation method were used to explain the observed photoisomerizations and ionochromic transformations. The obtained compounds represent multifunctional on-off-on molecular switches of optical and fluorescent properties upon sequential exposure to light and H+ or sequential addition of Fe2+ and AcO− ions. A combinatorial logic gate was designed based on the basis of these switching properties. 2025-02-06T07:52:06Z 2025-02-06T07:52:06Z 2025 Статья Rybalkin, V.P., Zmeeva, S.Y., Popova, L.L., Lisovin, A.V., Kletskii, M.E., Burov, O.N., Dubonosova, I.V., Demidov, O.P., Karlutova, O.Y., Shepelenko, E.N., Podshibyakin, V.A., Dubonosov, A.D., Bren, V.A. Photo- and ionochromic N-acylated 2-(aminomethylene)benzo[b]thiophene-3(2H)-ones containing a terpyridine receptor // Journal of Photochemistry and Photobiology A: Chemistry. - 2025. - 459. - статья № 116066. - DOI: 10.1016/j.jphotochem.2024.116066 https://dspace.ncfu.ru/handle/123456789/29631 en Journal of Photochemistry and Photobiology A: Chemistry application/pdf application/pdf Elsevier B.V.
institution	СКФУ
collection	Репозиторий
language	English
topic	Fluorescence Photochromism N → O acyl rearrangement Molecular switches
spellingShingle	Fluorescence Photochromism N → O acyl rearrangement Molecular switches Demidov, O. P. Демидов, О. П. Photo- and ionochromic N-acylated 2-(aminomethylene)benzo[b]thiophene-3(2H)-ones containing a terpyridine receptor
description	New photo- and ionochromic N-acylated 2-(aminomethylene)benzo[b]thiophen-3(2H)-ones containing a terpyridine receptor have been synthesized. They absorb in the visible region of the spectrum at 423–426 nm and exhibit emission at 463–468 nm. Their irradiation in acetonitrile with light of 436 nm leads to a multi-stage rearrangement, including Z/E isomerization about the C[dbnd]C bond, N → O migration of the acyl group and the formation of non-emissive O-acylated E-isomers, which were isolated preparatively. Their structure was established unambiguously by IR, 1H, 13C NMR spectroscopy and HR mass spectrometry. The reverse thermal reaction with O → N migration of the acyl group is catalyzed by acid catalysts. N-Acylated compounds in acetonitrile selectively form non-fluorescent complexes with Fe2+ cations, which is accompanied by the naked-eye effect with changing the color from yellow to maroon. A successful selective interaction with AcO− led to the restoration of the initial absorption and emission properties. Density functional theory (DFT) calculations at the M06-2X/def2-TZVP level with the PCM solvation method were used to explain the observed photoisomerizations and ionochromic transformations. The obtained compounds represent multifunctional on-off-on molecular switches of optical and fluorescent properties upon sequential exposure to light and H+ or sequential addition of Fe2+ and AcO− ions. A combinatorial logic gate was designed based on the basis of these switching properties.
format	Статья
author	Demidov, O. P. Демидов, О. П.
author_facet	Demidov, O. P. Демидов, О. П.
author_sort	Demidov, O. P.
title	Photo- and ionochromic N-acylated 2-(aminomethylene)benzo[b]thiophene-3(2H)-ones containing a terpyridine receptor
title_short	Photo- and ionochromic N-acylated 2-(aminomethylene)benzo[b]thiophene-3(2H)-ones containing a terpyridine receptor
title_full	Photo- and ionochromic N-acylated 2-(aminomethylene)benzo[b]thiophene-3(2H)-ones containing a terpyridine receptor
title_fullStr	Photo- and ionochromic N-acylated 2-(aminomethylene)benzo[b]thiophene-3(2H)-ones containing a terpyridine receptor
title_full_unstemmed	Photo- and ionochromic N-acylated 2-(aminomethylene)benzo[b]thiophene-3(2H)-ones containing a terpyridine receptor
title_sort	photo- and ionochromic n-acylated 2-(aminomethylene)benzo[b]thiophene-3(2h)-ones containing a terpyridine receptor
publisher	Elsevier B.V.
publishDate	2025
url	https://dspace.ncfu.ru/handle/123456789/29631
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Photo- and ionochromic N-acylated 2-(aminomethylene)benzo[b]thiophene-3(2H)-ones containing a terpyridine receptor

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