Excited-state structure of copper phenanthroline-based photosensitizers

Guda, Alexander; Windisch, Johannes; Probst, Benjamin; van Bokhoven, Jeroen A.; Alberto, Roger; Nachtegaal, Maarten; Chen, Lin X.; Smolentsev, Grigory

doi:10.1039/d1cp02823e

Excited-state structure of copper phenanthroline-based photosensitizers

Journal Article · Mon Nov 15 00:00:00 EST 2021 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d1cp02823e· OSTI ID:1982187

Guda, Alexander ^[1]; Windisch, Johannes ^[2]; ^[2]; ^[3]; ^[2]; Nachtegaal, Maarten ^[4]; ^[5]; ^[4]

Southern Federal University Rostov-on-Don (Russia)
University of Zurich (Switzerland)
Paul Scherrer Institute, Villigen (Switzerland); ETH Zurich (Switzerland)
Paul Scherrer Institute, Villigen (Switzerland)
Argonne National Laboratory (ANL), Argonne, IL (United States); Northwestern University, Evanston, IL (United States)

Cu diimine complexes present a noble metal free alternative to classical Ru, Re, Ir and Pt based photosensitizers in solution photochemistry, photoelectrochemical or dye-sensitized solar cells. Optimization of these dyes requires understanding of factors governing the key photochemical properties: excited state lifetime and emission quantum yield. The involvement of exciplex formation in the deactivation of the photoexcited state is a key question. Here, we investigate the excited-state structure of [Cu(dmp)₂]⁺ and [Cu(dsbtmp)₂]⁺ (dmp = 2,9-dimethyl-1,10-phenanthroline, dsbtmp = 2,9-di-sec-butyl-3,4,7,8-tetramethyl-1,10-phenanthroline) using pump–probe X-ray absorption spectroscopy (XAS) and DFT. Features of XAS that distinguish flattened tetrahedral site and 5-coordinated geometry with an additional solvent near Cu(II) center are identified. Pump–probe XAS demonstrates that for both complexes the excited state is 4-coordinated. For [Cu(dmp)₂]⁺ the exciplex is 0.24 eV higher in energy than the flattened triplet state, therefore it can be involved in deactivation pathways as a non-observable state that forms slower than it decays. For [Cu(dsbtmp)₂]⁺ the excited-state structure is characterized by Cu–N distances of 1.98 and 2.07 Å and minor distortions, leading to a 3 orders of magnitude longer excited-state lifetime.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Argonne Leadership Computing Facility (ALCF)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1982187

Alternate ID(s):: OSTI ID: 1832953

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 47 Vol. 23; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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