Toward Improved Charge Separation through Conformational Control in Copper Coordination Complexes

Griffin, Paul J.; Charette, Bronte J.; Burke, John H.; Vura-Weis, Josh; Schaller, Richard D.; Gosztola, David J.; Olshansky, Lisa

doi:10.1021/jacs.2c02580

Title: Toward Improved Charge Separation through Conformational Control in Copper Coordination Complexes

Journal Article · 28 June 2022 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.2c02580 · OSTI ID:1909014

Griffin, Paul J. ^[1]; Charette, Bronte J. ^[1];

^[1];

^[1]; Schaller, Richard D. ^[2];

^[2];

^[1]

University of Illinois at Urbana-Champaign, IL (United States)
Argonne National Laboratory (ANL), Lemont, IL (United States)

The continued development of solar energy as a renewable resource necessitates the design and study of new approaches to sustaining photodriven charge separation (CS). To this end, we present a bioinspired approach in which triggered conformational changes are used to control electron transfer (ET) events. We report, photo-induced conformational rearrangements of a ligand are translated into changes in the coordination geometry and environment about a bound metal ion. Taking advantage of the differential coordination properties of Cu^I and Cu^II, these dynamics facilitate intramolecular ET from Cu^I to the ligand to create a CS state. The synthesis and photophysical characterization of CuCl(dpaa^R) (dpaa = dipicolylaminoacetophenone, with R = H and OMe) is presented. These ligands incorporate a fluorophore into their framework that gives rise to a twisted intramolecular charge transfer (TICT) excited state. Excited state ligand twisting provides a tetragonal coordination geometry capable of capturing Cu^II in the CS state when an internal ortho-OMe binding site is present (as in dpaaOMe). We employ NMR, IR, EPR, and optical spectroscopies, X-ray diffraction, and electrochemical methods to establish the ground state properties of the Cu^I and Cu^II complexes. We then investigate the photophysical dynamics of these Cu^I complexes via time-resolved photoluminescence (TR-PL), and optical transient absorption (OTA) spectroscopies. We show that relative to controls lacking a TICT-active ligand, the lifetime of the CS state is enhanced ~1000-fold. Further, the presence of the ortho-OMe substituent greatly enhances the lifetime of the TICT* state and biases the coordination environment toward Cu^II. The presence of Cu^I decreases photoinduced degradation from 14 to <2% but does not result in significant quenching via ET. Factors affecting CS in these systems are discussed, laying the groundwork for our strategy toward solar energy conversion.

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Research Organization:: Argonne National Laboratory (ANL), Lemont, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1909014

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 27 Vol. 144; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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CCDC 2157318: Experimental Crystal Structure Determination J., Griffin, Paul; J., Charette, Bronte; H., Burke, John https://doi.org/10.5517/ccdc.csd.cc2bdvxj The current record is supplemented by this dataset	dataset	January 2022
CCDC 2157319: Experimental Crystal Structure Determination J., Griffin, Paul; J., Charette, Bronte; H., Burke, John https://doi.org/10.5517/ccdc.csd.cc2bdvyk The current record is supplemented by this dataset	dataset	January 2022
CCDC 2157320: Experimental Crystal Structure Determination J., Griffin, Paul; J., Charette, Bronte; H., Burke, John https://doi.org/10.5517/ccdc.csd.cc2bdvzl The current record is supplemented by this dataset	dataset	January 2022
CCDC 2157321: Experimental Crystal Structure Determination J., Griffin, Paul; J., Charette, Bronte; H., Burke, John https://doi.org/10.5517/ccdc.csd.cc2bdw0n The current record is supplemented by this dataset	dataset	January 2022
CCDC 2157322: Experimental Crystal Structure Determination J., Griffin, Paul; J., Charette, Bronte; H., Burke, John https://doi.org/10.5517/ccdc.csd.cc2bdw1p The current record is supplemented by this dataset	dataset	January 2022

Title: Toward Improved Charge Separation through Conformational Control in Copper Coordination Complexes

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