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Title: Next Generation Cuprous Phenanthroline MLCT Photosensitizer Featuring Cyclohexyl Substituents

Abstract

A new long–lived, visible light–absorbing homoleptic Cu(I) metal–to–ligand charge transfer (MLCT) photosensitizer [Cu(dchtmp)2]PF6 (dchtmp = 2,9–dicyclohexyl–3,4,7,8–tetramethyl–1,10–phenanthroline), has been synthesized, structurally characterized, and evaluated in terms of its molecular photophysics, electrochemistry, and electronic structure. Static and time–resolved transient absorption (TA) and photoluminescence (PL) spectroscopy measured on the title compound in CH2Cl2 (τ = 2.6 μs, ΦPL = 5.5%), CH3CN (τ = 1.5 μs, ΦPL = 2.6%), and THF (τ = 2.0 μs, ΦPL = 3.7%) yielded impressive photophysical metrics even when dissolved in Lewis basic solvents. The combined static spectroscopic data along with ultrafast TA experiments revealed that the pseudo–Jahn–Teller distortion and intersystem crossing dynamics in the MLCT excited state displayed characteristics of being sterically arrested throughout its evolution. Here, electrochemical and static PL data illustrate that [Cu(dchtmp)2]PF6 is a potent photoreductant (–1.77 V vs. Fc+/o in CH3CN) equal to or greater than all previously investigated homoleptic Cu(I) diimine complexes. Although we successfully prepared the cyclopentyl analog dcptmp (2,9–dicyclopentyl–3,4,7,8–tetramethyl–1,10–phenanthroline) using the same C–C radical coupling photochemistry as dchtmp, the corresponding Cu(I) complex could not be isolated due to the steric hinderance presented at the metal center. Ultimately, the successful preparation of [Cu(dchtmp)2]+ represents a major step forward for the design andmore » discovery of novel earth–abundant photosensitizers made possible through a newly conceived ligand synthetic strategy.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. North Carolina State Univ., Raleigh, NC (United States)
Publication Date:
Research Org.:
North Carolina State University, Raleigh, NC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1786981
Alternate Identifier(s):
OSTI ID: 1812207
Grant/Contract Number:  
SC0011979
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 60; Journal Issue: 12; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Diimides; Metal to ligand charge transfer; Ligands; Solvents; Excited states

Citation Formats

Rosko, Michael C., Wells, Kaylee A., Hauke, Cory E., and Castellano, Felix N. Next Generation Cuprous Phenanthroline MLCT Photosensitizer Featuring Cyclohexyl Substituents. United States: N. p., 2021. Web. doi:10.1021/acs.inorgchem.1c01242.
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Rosko, Michael C., Wells, Kaylee A., Hauke, Cory E., & Castellano, Felix N. Next Generation Cuprous Phenanthroline MLCT Photosensitizer Featuring Cyclohexyl Substituents. United States. https://doi.org/10.1021/acs.inorgchem.1c01242
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Rosko, Michael C., Wells, Kaylee A., Hauke, Cory E., and Castellano, Felix N. Mon . "Next Generation Cuprous Phenanthroline MLCT Photosensitizer Featuring Cyclohexyl Substituents". United States. https://doi.org/10.1021/acs.inorgchem.1c01242. https://www.osti.gov/servlets/purl/1786981.
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@article{osti_1786981,
title = {Next Generation Cuprous Phenanthroline MLCT Photosensitizer Featuring Cyclohexyl Substituents},
author = {Rosko, Michael C. and Wells, Kaylee A. and Hauke, Cory E. and Castellano, Felix N.},
abstractNote = {A new long–lived, visible light–absorbing homoleptic Cu(I) metal–to–ligand charge transfer (MLCT) photosensitizer [Cu(dchtmp)2]PF6 (dchtmp = 2,9–dicyclohexyl–3,4,7,8–tetramethyl–1,10–phenanthroline), has been synthesized, structurally characterized, and evaluated in terms of its molecular photophysics, electrochemistry, and electronic structure. Static and time–resolved transient absorption (TA) and photoluminescence (PL) spectroscopy measured on the title compound in CH2Cl2 (τ = 2.6 μs, ΦPL = 5.5%), CH3CN (τ = 1.5 μs, ΦPL = 2.6%), and THF (τ = 2.0 μs, ΦPL = 3.7%) yielded impressive photophysical metrics even when dissolved in Lewis basic solvents. The combined static spectroscopic data along with ultrafast TA experiments revealed that the pseudo–Jahn–Teller distortion and intersystem crossing dynamics in the MLCT excited state displayed characteristics of being sterically arrested throughout its evolution. Here, electrochemical and static PL data illustrate that [Cu(dchtmp)2]PF6 is a potent photoreductant (–1.77 V vs. Fc+/o in CH3CN) equal to or greater than all previously investigated homoleptic Cu(I) diimine complexes. Although we successfully prepared the cyclopentyl analog dcptmp (2,9–dicyclopentyl–3,4,7,8–tetramethyl–1,10–phenanthroline) using the same C–C radical coupling photochemistry as dchtmp, the corresponding Cu(I) complex could not be isolated due to the steric hinderance presented at the metal center. Ultimately, the successful preparation of [Cu(dchtmp)2]+ represents a major step forward for the design and discovery of novel earth–abundant photosensitizers made possible through a newly conceived ligand synthetic strategy.},
doi = {10.1021/acs.inorgchem.1c01242},
journal = {Inorganic Chemistry},
number = 12,
volume = 60,
place = {United States},
year = {Mon Jun 07 00:00:00 EDT 2021},
month = {Mon Jun 07 00:00:00 EDT 2021}
}
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