Halide impact on emission of mononuclear copper(I) complexes with pyrazolylpyrimidine and triphenylphosphine

Dalton Transactions : an International Journal of Inorganic Chemistry
Katerina A VinogradovaMark B Bushuev

Abstract

A series of mononuclear heteroleptic copper(I) halide complexes, [CuL(PPh3)X] (X = Cl, Br, I), based on 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(piperidin-1-yl)pyrimidine (L) and triphenylphosphine, have been synthesized by reaction between CuX (X = Cl, Br, I), L and PPh3 in a molar ratio of 1/1/1 in MeCN solutions. The copper atom, showing the distorted tetrahedral environment, is bound by the N,N-chelating ligand L, triphenylphosphine and a halide ion. The complexes [CuL(PPh3)Cl] and [CuL(PPh3)Br] are isostructural. In CH2Cl2 solutions, L and the complexes [CuL(PPh3)X] (X = Cl, Br, I) display a luminescence band with λ(max) = 377 nm and a lifetime of 1.9 ns (ligand-based luminescence (LL*)). However, the complex [CuL(PPh3)I] has an additional weak luminescence band with λ(max) = 681 nm and a lifetime of 96 ns of (3)MLCT origin. In the solid state, L shows the splitting of the luminescence band to λ(max) = 365 and 384 nm and a slight increase of the lifetime to 2.66 ns. Solid samples of the complexes [CuL(PPh3)X] demonstrate (3)MLCT luminescence bands at 620 nm (X = Cl), 605 nm (X = Br) and 559 nm (X = I) with lifetimes in the range 3.6-11.2 μs, whereas the LL* band (377 nm) is absent. Quantum yields and rate constants of radiative...Continue Reading

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Citations

Nov 26, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Katerina A VinogradovaMark B Bushuev
Dec 7, 2018·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Rong-Yan WangJi-Qing Xu
Jan 13, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Alexey S BerezinMark B Bushuev
Jun 17, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Katerina A VinogradovaMark B Bushuev

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