Photophysical properties of three-coordinate heteroleptic Cu(I) β-diketiminate triarylphosphine complexes

Kumar, Ashish; Kim, Dooyoung; Nguyen, Giao; Jiang, Chenggang; Chakraborty, Soumi; Teets, Thomas S.

doi:10.1039/d4dt02681k

Title: Photophysical properties of three-coordinate heteroleptic Cu(I) β-diketiminate triarylphosphine complexes

Journal Article · 18 November 2024 · Dalton Transactions

DOI: https://doi.org/10.1039/d4dt02681k · OSTI ID:2478437

Kumar, Ashish ^[1];

^[2];

^[2]

University of Houston, TX (United States); University of Houston
University of Houston, TX (United States)

A series of heteroleptic copper(I) β-diketiminate triarylphosphine complexes is reported, having the general formula Cu(R¹NacNac^R2)(PPh^X₃), where R¹NacNac^R2 is a substituted β-diketiminate and PPh^X₃ is a triphenylphosphine derivative. A total of five different R¹NacNac^R2 ligands and three different triarylphosphines are used to assemble the nine complexes. Here, the syntheses, X-ray crystal structures, cyclic voltammograms, and UV–vis absorption spectra of all compounds are described. Whereas most of the compounds are weakly luminescent or only luminesce at 77 K, the four complexes with the more sterically encumbered β-diketiminate ligands, with methyl or isopropyl substituents at the 2- and 6-positions of the N-phenyl rings, exhibit weak room-temperature photoluminescence with peaks between 519 and 566 nm and long excited-state lifetimes in the range of 15–70 μs. The sterically encumbering substituents in this subset have subtle effects on the UV–vis absorption maximum, which red shifts slightly as the steric bulk increases, as well as significant effects on the photoluminescence lifetime, which is observed to increase as the steric bulk is augmented. Substituents on the triarylphosphine also influence the excited-state dynamics in the bulky complexes, with the more electron-rich tris(4-methoxyphenyl)phosphine (PPh^OMe₃) giving longer-excited-state lifetimes compared to triphenylphosphine (PPh₃) when the same R¹NacNac^R2 ligand is used.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0023394

OSTI ID:: 2478437

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 1 Vol. 54; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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