Intra- vs Intermolecular Aurophilic Contacts in Dinuclear Gold(I) Compounds: Impact on the Population of the Triplet Excited State.
Inorg Chem
; 61(51): 20931-20941, 2022 Dec 26.
Article
in En
| MEDLINE
| ID: mdl-36512673
ABSTRACT
Two series of dinuclear gold(I) complexes that contain two Au-chromophore units (chromophore = dibenzofurane or dimethylfluorene) connected through a diphosphane bridge that differs in the flexibility and length (diphosphane = dppb for 1,4-bis(diphenylphosphino)butane, DPEphos for bis[(2-diphenylphosphino)phenyl]ether, xanthphos for 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, and BiPheP for 2,2'-bis(diphenylphosphino)-1,1'-biphenyl) have been synthesized and structurally characterized. Their photophysical properties have been carefully investigated, paying attention to the role of the presence, or absence, of aurophilic contacts and their nature (intra- or intermolecular character). This analysis was permitted due to the X-ray crystallographic determination of all of the structures of the compounds discussed herein. The quantum yields of the triplet population, ÏT, have been calculated by nanosecond-laser flash photolysis measurements, and we could determine the main role of the character of the aurophilic contacts in the resulting ÏT, being especially favored in the presence of intermolecular contacts. Time-dependent density functional theory (TD-DFT) calculations support the absorption and emission assignments and the shorter distance between S1 and the closest triplet excited state energy in the case of the compounds with a higher triplet-state population.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Inorg Chem
Year:
2022
Document type:
Article
Affiliation country:
Spain