Augmentation of inductive effects through short range intramolecular hydrogen bonds for the improvement of cooperativity of trimeric rosettes

PETELSKI, ANDRE NICOLAI NICOLAI; BUNDREA, TAMARA; PERUCHENA, NÉLIDA MARÍA

Molecular Systems Design & Engineering

RCS

Año: 2024

Cooperativity in hydrogen bonds can be crucial for the stabilization of supramolecular systems. In this contribution we propose a simple covalent modification within a trimeric rosette based on pyrazole that greatly improves its binding strength. Through dispersion corrected density functional theory, at the BLYP-D3(BJ)/6-311++(d,p) level, we show how an intramolecular hydrogen bond acts as a bridge between an electron-donating and an electron-withdrawing group by moving electron density from one group to the other one through the sigma electron system. This effect strongly enhances the inductive ability of the substituents, and further enhances the synergy of the cyclic trimer