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

Levi, Gianluca; Biasin, Elisa; Dohn, Asmus O.; Jónsson, Hannes

doi:10.1039/c9cp06086c

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

Journal Article · 04 December 2019 · Physical Chemistry Chemical Physics. PCCP

DOI: https://doi.org/10.1039/c9cp06086c · OSTI ID:1604759

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Univ. of Iceland, Reykjavik (Iceland)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)

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. We report 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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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: Icelandic Research Fund (IRF); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1604759

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 2 Vol. 22; ISSN 1463-9076; ISSN PPCPFQ

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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