Chromone-methanol clusters in the electronic ground and lowest triplet state: a delicate interplay of non-covalent interactions.
Phys Chem Chem Phys
; 24(25): 15208-15216, 2022 Jun 29.
Article
en En
| MEDLINE
| ID: mdl-35579075
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.
Texto completo:
1
Colección:
01-internacional
Base de datos:
MEDLINE
Asunto principal:
Cromonas
/
Metanol
Idioma:
En
Revista:
Phys Chem Chem Phys
Asunto de la revista:
BIOFISICA
/
QUIMICA
Año:
2022
Tipo del documento:
Article
País de afiliación:
Alemania
Pais de publicación:
Reino Unido