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.