Prominent enhancing effects of substituents on the strength of π···σ‐hole tetrel bond

Abstract

Abstract The potential applications of tetrel bonds involving π‐molecules in crystal materials and biological systems have prompted a theoretical investigation of the strength of π···σ‐hole tetrel bond in the systems with acetylene and its derivatives of CH 3 , AuPH 3 , Li, and Na as well as benzene as the π electron donors. A weak tetrel bond (Δ E < 15 kJ/mol) is found between acetylene and tetrel donor molecule TH 3 F (T = C, Si, Ge, Sn, and Pb). All substituents strengthen the π tetrel bond, but the electron‐donating sodium atoms have the largest enhancing effect and the interaction energy is up to about 24 kJ/mol in C 2 Na 2 ‐CH 3 F. The electron‐donating ability of the AuPH 3 fragment is intermediate between the methyl group and alkali metal atom. The origin of the stability of the π tetrel‐bonded complex is dependent on the nature of the tetrel donor and acceptor molecules and can be regulated by the substituents.