Theoretical study on the luminescence mechanism of AIEgens based HOFs adsorbing small molecules

Abstract

The diversity and reversibility of non-covalent interactions give hydrogen-bonded organic frameworks (HOFs) excellent gas adsorption and separation performance. Here we designed and synthesized HOFs based on aggregation-induced emission luminogens (AIEgens) to visualize the adsorption process of HOFs. We focused on the SQ system and its solvated SQ frameworks by different solvent conditions, employing the thermal vibration correlation function rate formalism coupled hybrid quantum mechanics/molecular mechanics protocol, to elucidate the relation between crystal structure and luminescent properties, as well as the specific adsorption ability of porous SQ HOF crystals on acetylene gas. It is found that compare to SQ crystal, the SQ symmetry in cocrystals are improved, and SQ-DCM cocrystal has the best symmetry. The absorption spectra of five SQ-based crystals are close to each other, and their emission spectra blueshifted from 540 nm of SQ, to 509 nm, 508 nm, 507 nm of SQ-EA, SQ-ACN, SQ-DCM, and then to 495 nm of SQ-TOL, consistent with experimental results. The kic of solvated cocrystals are about 1∼2 orders of magnitude smaller than that of non-solvated crystal SQ, resulting in significantly higher Φexp of solvated cocrystals than that of un-solvated one. DCM with small volume and C2v point group is more suitable for SQ crystal channel, indicating that small free region and shape matching are the key factors affecting the reversibility of crystallization of porous frames during solvent transport. Finally, the volume of the adsorbed gas C2H2 which is close to DCM, is more easily adsorbed by SQ framework. Our study offers theoretical insights into the design of porous crystals for gas adsorption and separation applications.