CC BY-NC-ND 4.0 · Organic Materials 2022; 4(03): 43-52
DOI: 10.1055/a-1883-6076
Supramolecular Chemistry
Original Article

Bifurcated Chalcogen Bonds Based on One σ-Hole

Saber Mehrparvar
a   Institut für Organische Chemie, Universität Duisburg-Essen, Universitätsstr. 7, 45117 Essen, Germany
,
Christoph Wölper
a   Institut für Organische Chemie, Universität Duisburg-Essen, Universitätsstr. 7, 45117 Essen, Germany
,
b   Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
,
a   Institut für Organische Chemie, Universität Duisburg-Essen, Universitätsstr. 7, 45117 Essen, Germany
› Author Affiliations


Abstract

Chalcogen bonds are noncovalent interactions and are increasingly coming into focus for the design of complex structures in research areas such as crystal engineering, molecular recognition and catalysis. Conceptionally, chalcogen bonds can be considered as interaction between one σ-hole and one Lewis base center. Herein, we analyze the interaction between bidentate chelating ligands having two nucleophilic centers with one single σ-hole of a chalcogenazole (two-lone-pair/one-σ-hole interactions). Referring to this, we show by quantum chemical calculations and X-ray studies that three bond types are possible: in the first case, a chalcogen bond is formed between the σ-hole and only one of the Lewis base centers. In the second case, a strong bond is formed by one nucleophilic center; the second center provides only a small amount of additional stabilization. In the third case, two equivalent bonds to the σ-hole are formed by both Lewis base centers. According to the calculations, the bifurcated bonds are stronger than simple chalcogen bonds and lead to a more rigid molecular arrangement in the complex.



Publication History

Received: 25 May 2022

Accepted after revision: 21 June 2022

Accepted Manuscript online:
23 June 2022

Article published online:
14 July 2022

© 2022. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes, or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/)

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