Chromone–methanol clusters in the electronic ground and lowest triplet state: a delicate interplay of non-covalent interactions

Abstract

Chromone offers two energetically almost equivalent docking sites for alcohol molecules, in which the hydroxyl group is hydrogen bonded to one of the free electron pairs of the carbonyl O atom. Here, the delicate balance between these two competing arrangements is studied by combining IR/R2PI and UV/IR/UV spectroscopy in a molecular beam supported by quantum-chemical calculations. Most interestingly, chromone undergoes an efficient intersystem crossing into the triplet manifold upon electronic excitation, so that the studies on aromatic molecule-solvent complexes are for the first time extended to such a cluster in a triplet state. As the lowest triplet state (T₁) is of ground state character, powerful energy decomposition approaches such as symmetry-adapted perturbation theory (SAPT) and local energy decomposition using the domain-based local pair natural orbital coupled–cluster method (DLPNO-CCSD(T)/LED) are applied. From the theoretical analysis we infer for the T₁ state a loss of planarity (puckering) of the 4-pyrone ring of the chromone unit, which considerably affects the interplay between different types of non-covalent interactions at the two possible binding sites.