Synergetic argentophilic and through space electronic interactions in a single-crystal-to-single-crystal photocycloaddition reaction: a mechanistic study

Ag(I) is able to mediate single-crystal-to-single-crystal transformation through [2+2] photocycloaddition to prepare high-conductivity materials. However, the intrinsic mechanism of Ag(I) mediation, the detailed photophysical and photochemical processes as well as the origin of the enhanced conductivity of nanocrystals are still unclear. In this work, the comprehensive kinetic scheme and regulation mechanism are established by the accurate QM/MM calculations at the CASPT2//CASSCF/AMBER level of theory with consideration of the crystal environment. We find that the argentophilic interaction and through space electronic interaction are the key factors that promote Ag(I)-mediated [2+2] PCA reactions and may account for the enhancement of conductivity. These mechanistic insights into the Ag(I)-regulated photo-dimerization in the crystal surrounding are beneficial for the design of the structurally and electrically favorable skeletons of a metal-organic coordination polymer.