Remarkably short intermolecular Se···Se contacts in Ni(II) diselenophosphinates: interplay of electrostatic and dispersion

Remarkably short intermolecular Se···Se contacts in Ni(II) diselenophosphinates: interplay of electrostatic and dispersion Научная публикация

Журнал

Inorganic chemistry frontiers
ISSN: 2052-1553 , E-ISSN: 2052-1545

Вых. Данные

Год: 2025, Том: 12, Номер: 4, Страницы: 1568-1578 Страниц : 11 DOI: 10.1039/d4qi03204g

Авторы

Tupikina Elena Yu. ¹ , Davydova Maria ² , Mulloyarova Valeriya V. ¹ , Sukhikh Taisiya Sergeevna ² , Samsonenko Denis G. ² , Tolstoy Peter ¹ , Artem'ev Alexander ²

Организации

1	Institute of Chemistry, St. Petersburg State University, 198504 St. Petersburg, Russian Federation
2	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3, Akad. Lavrentiev Ave., Novosibirsk 630090, Russian Federation

We report the discovery of remarkably short intermolecular Se···Se contacts (3.242–3.751 Å) and a novel supramolecular Se/Se\Se/Se zigzag pattern in Ni(II) diselenophosphinate complexes. The monoclinic polymorph of [Ni(Se2PPh2)2], along with [Ni(Se2PPh2)2(Pz)2] and the 1D polymer Ni(Se2PPPh2)2(3,3’-bipy)]n, exhibit this zigzag pattern with one short (avg. 3.35 Å) and two longer (avg. 3.68 Å) Se···Se contacts between adjacent NiP2Se4 units. In contrast, the orthorhombic [Ni(Se2PPh2)2] and the 1D polymer [Ni(Se2PPPh2)2(4,4’-bipy)]n display chain-like intermolecular Se···Se contacts of about 3.51 Å. Employing a multifaceted approach, we elucidate the nature of the interactions, distinguishing between electrostatic and dispersion contributions. Using theoretical methods (DFT-DKH for geometry optimization; electron density, ESP, ELF, SAPT0 for analysis), we find that short Se···Se interactions (< 90%ΣrvdW(Se···Se)) are governed primarily by dispersion forces, whereas longer Se···Se contacts (> 90% ΣrvdW(Se···Se)) are mainly attributed to electrostatic forces, typical of σ-hole interactions. Notably, we document an unprecedented Se···Se contact of 3.242 Å, which, to our knowledge, is the shortest proven non-covalent Se···Se interaction reported to date. This finding not only confirms the existence of Se···Se interactions, but also highlights their potential strength and importance in coordination chemistry, an aspect that has not been thoroughly explored in previous studies.

Tupikina E.Y. , Davydova M. , Mulloyarova V.V. , Sukhikh T.S. , Samsonenko D.G. , Tolstoy P. , Artem'ev A.
Remarkably short intermolecular Se···Se contacts in Ni(II) diselenophosphinates: interplay of electrostatic and dispersion
Inorganic chemistry frontiers. 2025. V.12. N4. P.1568-1578. DOI: 10.1039/d4qi03204g WOS OpenAlex

Поступила в редакцию:	12 дек. 2024 г.
Принята к публикации:	26 дек. 2024 г.
Опубликована online:	31 дек. 2024 г.
Опубликована в печати:	21 февр. 2025 г.

Web of science:	WOS:001395991800001
OpenAlex:	W4405924914

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