Long Excited-State Lifetimes in Three-Coordinate Copper(I) Complexes via Triplet–Triplet Energy Transfer to Pyrene-Decorated Isocyanides

Kim, Dooyoung; Rosko, Michael C.; Castellano, Felix N.; Gray, Thomas G.; Teets, Thomas S.

doi:10.1021/jacs.4c04288

Long Excited-State Lifetimes in Three-Coordinate Copper(I) Complexes via Triplet–Triplet Energy Transfer to Pyrene-Decorated Isocyanides

Journal Article · Tue Jul 02 00:00:00 EDT 2024 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.4c04288· OSTI ID:2439771

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University of Houston, TX (United States); University of Houston
North Carolina State University, Raleigh, NC (United States)
Case Western Reserve University, Cleveland, OH (United States)
University of Houston, TX (United States)

There has been much effort to improve excited-state lifetimes in photosensitizers based on earth-abundant first-row transition metals. Copper(I) complexes have gained significant attention in this field, and in most cases, sterically driven approaches are used to optimize their lifetimes. This study presents a series of three-coordinate copper(I) complexes (Cu1–Cu3) where the excited-state lifetime is extended by triplet–triplet energy transfer. The heteroleptic compounds feature a cyclohexyl-substituted β-diketiminate (CyNacNac^Me) paired with aryl isocyanide ligands, giving the general formula Cu(CyNacNac^Me)(CN-Ar) (CN-dmp = 2,6-dimethylphenyl isocyanide for Cu1; CN-pyr = 1-pyrenyl isocyanide for Cu2; CN-dmp-pyr = 2,6-dimethyl-4-(1-pyrenyl)phenyl isocyanide for Cu3). The nature, energies, and dynamics of the low-energy triplet excited states are assessed with a combination of photoluminescence measurements at room temperature and 77 K, ultrafast transient absorption (UFTA) spectroscopy, and DFT calculations. The complexes with the pyrene-decorated isocyanides (Cu2 and Cu3) exhibit extended excited-state lifetimes resulting from triplet–triplet energy transfer (TTET) between the short-lived charge-transfer excited state (³CT) and the long-lived pyrene-centered triplet state (³pyr). This TTET process is irreversible in Cu3, producing exclusively the ³pyr state, and in Cu2, the ³CT and ³pyr states are nearly isoenergetic, enabling reversible TTET and long-lived ³CT luminescence. The improved photophysical properties in Cu2 and Cu3 result in improvements in activity for both photocatalytic stilbene E/Z isomerization via triplet energy transfer and photoredox transformations involving hydrodebromination and C–O bond activation. Furthermore, these results illustrate that the extended excited-state lifetimes achieved through TTET result in newly conceived photosynthetically relevant earth-abundant transition metal complexes.

View Accepted Manuscript (DOE)

Research Organization:: University of Houston, TX (United States)

Sponsoring Organization:: Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0011979; SC0023394

OSTI ID:: 2439771

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 28 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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CCDC 2332964: Experimental Crystal Structure Determination Dooyoung, Kim,; C., Rosko, Michael; N., Castellano, Felix https://doi.org/10.5517/ccdc.csd.cc2j9mxd The current record is supplemented by this dataset	dataset	January 2024
CCDC 2332965: Experimental Crystal Structure Determination Dooyoung, Kim,; C., Rosko, Michael; N., Castellano, Felix https://doi.org/10.5517/ccdc.csd.cc2j9myf The current record is supplemented by this dataset	dataset	January 2024
CCDC 2332966: Experimental Crystal Structure Determination Dooyoung, Kim,; C., Rosko, Michael; N., Castellano, Felix https://doi.org/10.5517/ccdc.csd.cc2j9mzg The current record is supplemented by this dataset	dataset	January 2024

Long Excited-State Lifetimes in Three-Coordinate Copper(I) Complexes via Triplet–Triplet Energy Transfer to Pyrene-Decorated Isocyanides

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