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

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 d...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2020-01, Vol.22 (2), p.748-757
Main Authors: Levi, Gianluca, Biasin, Elisa, Dohn, Asmus O, Jónsson, Hannes
Format: Article
Language:English
Subjects:
Acetonitrile
Alternative energy sources
Angles (geometry)
Cartesian coordinates
Coordination compounds
Copper
Dynamics
Electron density
Electronic structure
Energy conversion efficiency
Excitation
Flattening
Initial conditions
Jahn-Teller effect
Mathematical analysis
Molecular orbitals
Molecular structure
Parameters
Quantum efficiency
Ruthenium
Simulation
Solar energy conversion
Solvents
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Summary: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 ] + . QM/MM direct dynamics simulations in acetonitrile reveal the interplay between solvent and conformational effects in the photoinduced ultrafast flattening of a copper photosensitizer.
ISSN:1463-9076
1463-9084
DOI:10.1039/c9cp06086c