Issue 47, 2018

Cooperative effects between π-hole triel and π-hole chalcogen bonds

Abstract

MP2/aug-cc-pVTZ calculations have been performed on π-hole triel- and chalcogen-bonded complexes involving a heteroaromatic compound. These complexes are very stable with large interaction energy up to −47 kcal mol−1. The sp2-hybridized nitrogen atom engages in a stronger π-hole bond than the sp-hybridized species although the former has smaller negative electrostatic potential. The sp2-hybridized oxygen atom in 1,4-benzoquinone is a weaker electron donor in the π-hole bond than the sp2-hybridized nitrogen atom. The π-hole triel bond is stronger than the π-hole chalcogen bond. A clear structural deformation is found for the triel or chalcogen donor molecule in these π-hole-bonded complexes. The triel bond exhibits partially covalent interaction, whereas the chalcogen bond exhibits covalent interaction in the SO3 complexes of pyrazine and pyridine derivatives with a sp2-hybridized nitrogen atom. Intermolecular charge transfer (>0.2e) occurs to a considerable extent in these complexes. In ternary complexes involving an aromatic compound, wherein a triel bond and a chalcogen bond coexist, both the interactions are weakened or strengthened when the central aromatic molecule acts as a double Lewis base or plays a dual role of both a base and an acid. Both electrostatic and charge transfer effects have important contributions toward changes in the strength of both interactions.

Graphical abstract: Cooperative effects between π-hole triel and π-hole chalcogen bonds

Supplementary files

Article information

Article type
Paper
Submitted
14 May 2018
Accepted
10 Jul 2018
First published
25 Jul 2018
This article is Open Access
Creative Commons BY-NC license

RSC Adv., 2018,8, 26580-26588

Cooperative effects between π-hole triel and π-hole chalcogen bonds

J. Zhang, W. Li, J. Cheng, Z. Liu and Q. Li, RSC Adv., 2018, 8, 26580 DOI: 10.1039/C8RA04106G

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