Impact of the Anthryl Linking Mode on the Photophysics and Excited-State Dynamics of Re(I) Complexes [ReCl(CO)₃(4'-An-terpy-κ²N)].

ABSTRACT: Rhenium(I) complexes with 2,2':6',2″-terpyridines (terpy) substituted with 9-anthryl (1) and 2-anthryl (2) were synthesized, and the impact of the anthryl linking mode on the ground- and excited-state properties of resulting complexes [ReCl(CO)₃(4'-An-terpy-κ²N)] (An─anthryl) was investigated using a combination of steady-state and time-resolved optical techniques accompanied by theoretical calculations. Different attachment positions of anthracene modify the overlap between the molecular orbitals and thus the electronic coupling of the anthracene and {ReCl(CO)₃(terpy-κ²N)} chromophores. Following the femtosecond transient absorption, the lowest triplet excited state of both complexes was found to be localized on the anthracene chromophore. The striking difference between 1 and 2 concerns the triplet-state formation dynamics. A more planar geometry of 2-anthryl-terpy (2), and thus better electronic communication between the anthracene and {ReCl(CO)₃(terpy-κ²N)} chromophores, facilitates the formation of the ³An triplet state. In steady-state photoluminescence spectra, the population ratio of ³MLCT and ³An was found to be dependent not only on the anthryl linking mode but also on solvent polarity and excitation wavelengths. In dimethyl sulfoxide (DMSO), compounds 1 and 2 excited with λ_exc > 410 nm show both ³MLCT and ³An emissions, which are rarely observed. Additionally, the abilities of the designed complexes for ¹O₂ generation and light emission under the external voltage were preliminary examined.

SUBMITTER: Malecka M 

PROVIDER: S-EPMC9516691 | biostudies-literature | 2022 Sep

REPOSITORIES: biostudies-literature