Design of Supramolecular Tectons via Intramolecular S/Se‧‧‧ONO2 Chalcogen Bonding

Design of Supramolecular Tectons via Intramolecular S/Se‧‧‧ONO2 Chalcogen Bonding Научная публикация

Журнал

Asian Journal of Organic Chemistry
ISSN: 2193-5815 , E-ISSN: 2193-5807

Вых. Данные

Год: 2025, Номер статьи : e202500088, Страниц : DOI: 10.1002/ajoc.202500088

Авторы

Semenov Artem V. ¹ , Katlenok Eugene A. ¹ , Starosotnikov Alexey M. ² , Bastrakov Maxim A. ² , Minyaev Mikhail E. ² , Zelenkov Lev E. ³ , Shetnev Anton A. ⁴ , Sapegin Alexander V. ¹ , Boyarskiy Vadim P. ¹ , Baykov Sergey ⁵

Организации

1	Saint Petersburg State University: Sankt-peterburgskij gosudarstvennyj universitet Institute of Chemistry RUSSIAN FEDERATION
2	Zelinsky Institute of Organic Chemistry RAS: FGBUN Institut organiceskoj himii imeni N D Zelinskogo Rossijskoj akademii nauk - RUSSIAN FEDERATION
3	Harbin Engineering University - CHINA
4	Ushinsky Yaroslavl State Pedagogical University - RUSSIAN FEDERATION
5	Saint Petersburg University: Sankt-peterburgskij gosudarstvennyj universitet Institute of Chemistry 26 Universitetsky Pr 198504 Saint Petersburg RUSSIAN FEDERATION

A series of 2-nitrochalcogenocyanato(hetero)arenes were synthesized by the reaction of 2-nitrohalo(hetero)arenes with potassium thio- or selenocyanate. These compounds were characterized by NMR spectroscopy, high-resolution mass spectrometry, and X-ray crystallography. In the obtained crystal structures, strong intramolecular Ch⋅⋅⋅ONO2 (Ch=S, Se) chalcogen bonds between the chalcogen atom of the chalcogenocyanate moiety and the nitro group were revealed. These interactions prevent rotation of the nitro group, and thus stabilize the obtained 2-nitrochalcogenocyanato(hetero)arenes in a distorted planar geometry. In addition, intermolecular Ch⋅⋅⋅N chalcogen bonds were observed in some structures. Both intra- and intermolecular interactions were studied using methods based on first-principles and DFT approaches (e. g. QTAIM, IGMH, ELF, NBO). Two of the synthesized chalcogenocyanates namely, 4-nitro-5-thiocyanatophthalonitrile (2a) and 4-nitro-5-selenocyanatophthalonitrile (2b) were identified as promising supramolecular tectons for cocrystallizations with aromatic hydrocarbons, and four new cocrystals (2 a⋅PhMe, 2 a⋅o-XylH, 2 a⋅p-XylH, and 2 b⋅1.5(p-XylH)) were obtained. X-ray diffraction studies of these cocrystals demonstrated that in all cases molecules of the phthalonitrile (2 a or 2 b) and the corresponding hydrocarbon are packed into infinity columnar stacks via π⋅⋅⋅π interactions, whereas intermolecular Ch⋅⋅⋅O/N ChBs bound them to form the final supramolecular architecture.

Semenov A.V. , Katlenok E.A. , Starosotnikov A.M. , Bastrakov M.A. , Minyaev M.E. , Zelenkov L.E. , Shetnev A.A. , Sapegin A.V. , Boyarskiy V.P. , Baykov S.
Design of Supramolecular Tectons via Intramolecular S/Se‧‧‧ONO2 Chalcogen Bonding
Asian Journal of Organic Chemistry. 2025. e202500088 . DOI: 10.1002/ajoc.202500088 WOS Scopus OpenAlex

Web of science:	WOS:001445927600001
Scopus:	2-s2.0-105000455751
OpenAlex:	W4408307173

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