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

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

Journal

Dalton Transactions
ISSN: 1477-9226 , E-ISSN: 1477-9234

Output data

Year: 2014, Volume: 43, Number: 7, Pages: 2953-2960 Pages count : DOI: 10.1039/c3dt53040j

Authors

Vinogradova Katerina A. ¹ , Plyusnin Victor F. ^2,3 , Kupryakov Arkady S. ^2,3 , Rakhmanova Marianna I. ¹ , Pervukhina Natalia V. ¹ , Naumov Dmitrii Yu. ¹ , Sheludyakova Lilia A. ^1,2 , Nikolaenkova Elena B. ⁴ , Krivopalov Viktor P. ⁴ , Bushuev Mark B. ^1,2

Affiliations

1	(Данные Web of science) Russian Acad Sci, Siberian Branch, Nikolaev Inst Inorgan Chem, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Natl Res Univ, Dept Nat Sci, Novosibirsk 630090, Russia
3	(Данные Web of science) Russian Acad Sci, Siberian Branch, Inst Chem Kinet & Combust, Novosibirsk 630090, Russia
4	(Данные Web of science) Russian Acad Sci, Siberian Branch, NN Vorozhtsov Novosibirsk Inst Organ Chem, Novosibirsk 630090, Russia

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 lambda(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 lambda(max) = 681 nm and a lifetime of 96 ns of (MLCT)-M-3 origin. In the solid state, L shows the splitting of the luminescence band to lambda(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 (MLCT)-M-3 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 mu s, whereas the LL* band (377 nm) is absent. Quantum yields and rate constants of radiative and nonradiative processes were determined in CH2Cl2 solutions and in the solid state for all complexes. The luminescence quantum yield and lifetimes for the solid samples increase in the order [CuL(PPh3)Cl] < [CuL(PPh3) Br] < [CuL(PPh3)I]. This is due to the increase of radiative decay and simultaneous suppression of nonradiative decay. The complex [CuL(PPh3)I] shows a high quantum yield of 29.4% and an excited state lifetime of 11.2 mu s.

Vinogradova K.A. , Plyusnin V.F. , Kupryakov A.S. , Rakhmanova M.I. , Pervukhina N.V. , Naumov D.Y. , Sheludyakova L.A. , Nikolaenkova E.B. , Krivopalov V.P. , Bushuev M.B.
Halide impact on emission of mononuclear copper(I) complexes with pyrazolylpyrimidine and triphenylphosphine
Dalton Transactions. 2014. V.43. N7. P.2953-2960. DOI: 10.1039/c3dt53040j WOS Scopus РИНЦ

Web of science	WOS:000330118000031
Scopus	2-s2.0-84892942150
Elibrary	21863472
OpenAlex	W1974743713