TY - JOUR

T1 - Halide Complexes of 5,6-Dicyano-2,1,3-Benzoselenadiazole with 1 : 4 Stoichiometry: Cooperativity between Chalcogen and Hydrogen Bonding

AU - Radiush, Ekaterina A

AU - Wang, Hui

AU - Chulanova, Elena A

AU - Ponomareva, Yana A

AU - Li, Bin

AU - Wei, Qiao Yu

AU - Salnikov, Georgy E

AU - Petrakova, Svetlana Yu

AU - Semenov, Nikolay A

AU - Zibarev, Andrey V

N1 - The Supporting information for this article contains XRD, solutionand solid-state UV-Vis, variable-temperature 35 Cl and 77 Se NMR, DFT, TD-DFT, QTAIM, EDD and EDA data. Within the Supporting Information, the authorshavecitedadditionalreferences (Ref.[164–169]). © 2023 Wiley-VCH GmbH.

PY - 2023/11

Y1 - 2023/11

N2 - The [M4 -Hal]- (M=the title compound; Hal=Cl, Br, and I) complexes were isolated in the form of salts of [Et4 N]+ 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 [Et4 N]+ [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 [Et4 N]+ [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.

AB - The [M4 -Hal]- (M=the title compound; Hal=Cl, Br, and I) complexes were isolated in the form of salts of [Et4 N]+ 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 [Et4 N]+ [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 [Et4 N]+ [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.

KW - chalcogen bonding

KW - chalcogenadiazoles

KW - cooperativity

KW - hydrogen bonding

KW - noncovalent interactions

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85174247941&origin=inward&txGid=609d08b734e554ee41a0b64135debede

UR - https://www.mendeley.com/catalogue/52800254-a836-3d0d-847b-440014b24d19/

U2 - 10.1002/cplu.202300523

DO - 10.1002/cplu.202300523

M3 - Article

C2 - 37750466

VL - 88

JO - ChemPlusChem

JF - ChemPlusChem

SN - 2192-6506

IS - 11

M1 - e202300523

ER -