Issue 2, 2020

On the interplay of solvent and conformational effects in simulated excited-state dynamics of a copper phenanthroline photosensitizer

Abstract

Copper(I) bis-phenanthroline complexes represent Earth-abundant alternatives to ruthenium-based sensitizers for solar energy conversion and photocatalysis. Improved understanding of the solvent-mediated excited-state structural dynamics can help optimize their photoconversion efficiency. Through direct dynamics simulations in acetonitrile and excited-state minimum energy path calculations in vacuum, we uncover the mechanism of the photoinduced flattening motion of the prototypical system [Cu(dmphen)2]+ (dmphen = 2,9-dimethyl-1,10-phenanthroline). We find that the ligand distortion is a two-step process in acetonitrile. The fast component (∼110 fs) is due to spontaneous pseudo Jahn–Teller instability and is largely solvent independent, while the slow component (∼1.2 ps) arises from the mutual interplay between solvent molecules closely approaching the metal center and rotation of the methyl substituents. These results shed new light on the influence of a donor solvent such as acetonitrile and methyl substituents on the flattening dynamics of [Cu(dmphen)2]+.

Graphical abstract: On the interplay of solvent and conformational effects in simulated excited-state dynamics of a copper phenanthroline photosensitizer

Supplementary files

Article information

Article type
Paper
Submitted
08 Nov 2019
Accepted
05 Dec 2019
First published
05 Dec 2019

Phys. Chem. Chem. Phys., 2020,22, 748-757

On the interplay of solvent and conformational effects in simulated excited-state dynamics of a copper phenanthroline photosensitizer

G. Levi, E. Biasin, A. O. Dohn and H. Jónsson, Phys. Chem. Chem. Phys., 2020, 22, 748 DOI: 10.1039/C9CP06086C

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