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Chalcogen-bonded donor-acceptor complexes of 5,6-dicyano[1,2,5]selenadiazolo[3,4-b]pyrazine with halide ions Научная публикация

Журнал New Journal of Chemistry
ISSN: 1144-0546
Вых. Данные Год: 2022, Том: 46, Страницы: 14490-14501 Страниц : 12 DOI: 10.1039/d2nj02345h
Авторы Radiush Ekaterina A. 1 , Pritchina Elena A. 2,3 , Chulanova Elena A. 1 , Dmitriev Alexey A. 2,4 , Bagryanskaya Irina Yu. 1 , Slawin Alexandra M.Z. 5 , Woollins J.Derek 5,6 , Gritsan Nina P. 2 , Zibarev Andrey V. 1 , Semenov Nikolay A. 1
Организации
1 N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian Branch of Russian Academy of Sciences
2 Voevodsky Institute of Chemical Kinetics and Combustion, SB RAS
3 Novosibirsk State University
4 Novosibirsk State University
5 University of St Andrews
6 Khalifa University of Science and Technology

Информация о финансировании (1)

1 Российский Научный Фонд 21-73-10291

Реферат: New complexes of 5,6-dicyano[1,2,5]selenadiazolo[3,4-b]pyrazine 1 with halide anions X− (X = Cl, Br, I) are prepared. With XRD, DFT, QTAIM and NBO, it is found that the complexes are formed via Se–X− chalcogen bonding. Diffuse reflectance spectroscopy of polycrystalline samples and UV/Vis spectroscopy of solutions of [1–X]− reveal significant spectral changes upon complexation. According to time-dependent DFT, these changes are caused by the appearance of charge transfer bands (p-AO(X) → LUMO(1)) in the visible region. The equilibrium constants for complex formation were measured with UV/Vis spectrophotometric titration and found to be significantly lower than those reported for structurally similar complexes of 3,4-dicyano-1,2,5-selena(tellura)diazoles, which indicates relatively weak chalcogen bonding in [1–X]−. Dispersion-corrected DFT reproduces well the Gibbs free energies of complexation. The QTAIM descriptors and NBO analyses using second-order perturbation theory suggest that the Se–X− chalcogen bonding in the studied complexes is predominantly electrostatic and dispersive in nature with a small but significant contribution from donor–acceptor (or orbital) interactions. The strongest contribution to the latter comes from negative hyperconjugation, i.e. donation of the electron density of the lone-pair of X− onto the σ*–MO of the Se–N bond of 1.
Библиографическая ссылка: Radiush E.A. , Pritchina E.A. , Chulanova E.A. , Dmitriev A.A. , Bagryanskaya I.Y. , Slawin A.M.Z. , Woollins J.D. , Gritsan N.P. , Zibarev A.V. , Semenov N.A.
Chalcogen-bonded donor-acceptor complexes of 5,6-dicyano[1,2,5]selenadiazolo[3,4-b]pyrazine with halide ions
New Journal of Chemistry. 2022. V.46. P.14490-14501. DOI: 10.1039/d2nj02345h WOS OpenAlex
Даты:
Поступила в редакцию: 12 мая 2022 г.
Принята к публикации: 1 июл. 2022 г.
Опубликована online: 4 июл. 2022 г.
Идентификаторы БД:
Web of science: WOS:000823756000001
OpenAlex: W4285271265
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БД Цитирований
OpenAlex 11
Web of science 10
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