Halide Complexes of 5,6‐Dicyano‐2,1,3‐Benzoselenadiazole with 1 : 4 Stoichiometry: Cooperativity between Chalcogen and Hydrogen Bonding

Halide Complexes of 5,6‐Dicyano‐2,1,3‐Benzoselenadiazole with 1 : 4 Stoichiometry: Cooperativity between Chalcogen and Hydrogen Bonding Full article

Journal

ChemPlusChem
ISSN: 2192-6506

Output data

Year: 2023, Volume: 88, Number: 11, Article number : e202300523, Pages count : 11 DOI: 10.1002/cplu.202300523

Authors

Radiush Ekaterina A. ¹ , Wang Hui ² , Chulanova Elena A. ^1,3 , Ponomareva Yana A. ^1,4 , Li Bin ² , Wei Qiao Yu ² , Salnikov Georgy E. ¹ , Petrakova Svetlana Yu. ¹ , Semenov Nikolay A. ¹ , Zibarev Andrey V. ¹

Affiliations

1	Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk, Russia
2	School of Physical Science and Technology, Southwest Jiaotong University, 610031 Chengdu, P. R. China
3	Current address: Institute for Applied Physics, University of Tübingen, 72076 Tübingen, Germany
4	Department of Natural Sciences, National Research University – Novosibirsk State University, 630090 Novosibirsk, Russia

The [M4−Hal]− (M=the title compound; Hal=Cl, Br, and I) complexes were isolated in the form of salts of [Et4N]+ cation and characterized by XRD, NMR, UV-Vis, DFT, QTAIM, EDD, and EDA. Their stoichiometry is caused by a cooperative interplay of σ-hole-driven chalcogen (ChB) and hydrogen (HB) bondings. In the crystal, [M4−Hal]− are connected by the π-hole-driven ChB; overall, each [Hal]− is six-coordinated. In the ChB, the electrostatic interaction dominates over orbital and dispersion interactions. In UV-Vis spectra of the M+[Hal]− solutions, ChB-typical and [Hal]−-dependent charge-transfer bands are present; they reflect orbital interactions and allow identification of the individual [Hal]−. However, the structural situation in the solutions is not entirely clear. Particularly, the UV-Vis spectra of the solutions are different from the solid-state spectra of the [Et4N]+[M4−Hal]−; very tentatively, species in the solutions are assigned [M−Hal]−. It is supposed that the formation of the [M4−Hal]− proceeds during the crystallization of the [Et4N]+[M4−Hal]−. Overall, M can be considered as a chromogenic receptor and prototype sensor of [Hal]−. The findings are also useful for crystal engineering and supramolecular chemistry.

Radiush E.A. , Wang H. , Chulanova E.A. , Ponomareva Y.A. , Li B. , Wei Q.Y. , Salnikov G.E. , Petrakova S.Y. , Semenov N.A. , Zibarev A.V.
Halide Complexes of 5,6‐Dicyano‐2,1,3‐Benzoselenadiazole with 1 : 4 Stoichiometry: Cooperativity between Chalcogen and Hydrogen Bonding
ChemPlusChem. 2023. V.88. N11. e202300523 :1-11. DOI: 10.1002/cplu.202300523 WOS Scopus РИНЦ

Submitted:	Sep 19, 2023
Published online:	Sep 26, 2023
Published print:	Nov 1, 2023

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