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

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


Title: On the interplay of solvent and conformational effects in simulated excited-state dynamics of a copper phenanthroline photosensitizer
Author: Levi, Gianluca   orcid.org/0000-0002-4542-0653
Biasin, Elisa
Dohn, Asmus O.
Jónsson, Hannes   orcid.org/0000-0001-8285-5421
Date: 2020
Language: English
Scope: 748-757
University/Institute: Háskóli Íslands
University of Iceland
School: Verkfræði- og náttúruvísindasvið (HÍ)
School of Engineering and Natural Sciences (UI)
Department: Raunvísindastofnun (HÍ)
Science Institute (UI)
Raunvísindadeild (HÍ)
Faculty of Physical Sciences (UI)
Series: Physical Chemistry Chemical Physics;22
ISSN: 1463-9076
1463-9084 (eISSN)
DOI: 10.1039/c9cp06086c
Subject: Kopar; Efnasambönd
URI: https://hdl.handle.net/20.500.11815/1488

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Citation:

Levi, G., Biasin, E., Dohn, A. O., & Jónsson, H. (2020). On the interplay of solvent and conformational effects in simulated excited-state dynamics of a copper phenanthroline photosensitizer. Physical Chemistry Chemical Physics, 22(2), 748-757. doi:10.1039/C9CP06086C

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]+.

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