TY - JOUR

T1 - Heteroleptic ionic copper(I) complexes based on pyrazolo[1,5-A] [1,10]phenanthrolines: synthesis, structure, and photoluminescence

AU - Виноградова, Катерина Александровна

AU - Рахманова, Мариана Ивановна

AU - Тайгина, Марина Дмитриевна

AU - Первухина, Наталья Викторовна

AU - Naumov, D. Yu

AU - Санникова, Виктория Александровна

AU - Филиппов, Игорь Романович

AU - Колыбалов, Дмитрий Сергеевич

AU - Воробьев, Алексей Юрьевич

N1 - The study was supported by the Russian Science Foundation (Project no. 22-73-00255).

PY - 2024

Y1 - 2024

N2 - Heteroleptic copper(I) tetrafluoroborate complexes with pyrazolo[1,5-a][1,10]phenanthrolines (Ln, n = 1–3) and bis[(2-diphenylphosphino)phenyl] ether (POP) were synthesized and structurally characterized. The coordination compounds with the general formula [CuLn(POP)]BF4·Solv (n =1, Solv =0.5MeCN, complex I; n = 2, Solv = 0.5CH2Cl2, complex II; n = 3, Solv = 1.25Et2O, complex III·Et2O) were prepared by the reaction of CuBF4 with Ln and POP in organic solvents (MeCN/CH2Cl2/Et2O) at 1 : 1 : 1 molar ratio. Compound III·Et2O gradually loses solvate molecules to be converted to the complex [CuL3(POP)]BF4 (III). According to single-crystal X-ray diffraction data, the complexes (I, II, III·Et2O) are ionic; the copper atom in the [CuLn(POP)]+ cation is located in a distorted tetrahedral environment (CuN2P2). The photoluminescence properties of the obtained complexes (I–III) were studied in the solid state and in solution. In the absorption spectra of the complexes, a charge transfer band is observed at 380–385 nm; excitation in this range gives rise to two emission bands at 480 and 650 nm in solution. In the solid state, the complexes show photoluminescence only in the red range (λmax = 600–610 nm) with microsecond lifetimes. It was Found that complexes I and III with a more regular tetrahedral environment have quantum yields an order of magnitude higher than the quantum yield observd for complex II.

AB - Heteroleptic copper(I) tetrafluoroborate complexes with pyrazolo[1,5-a][1,10]phenanthrolines (Ln, n = 1–3) and bis[(2-diphenylphosphino)phenyl] ether (POP) were synthesized and structurally characterized. The coordination compounds with the general formula [CuLn(POP)]BF4·Solv (n =1, Solv =0.5MeCN, complex I; n = 2, Solv = 0.5CH2Cl2, complex II; n = 3, Solv = 1.25Et2O, complex III·Et2O) were prepared by the reaction of CuBF4 with Ln and POP in organic solvents (MeCN/CH2Cl2/Et2O) at 1 : 1 : 1 molar ratio. Compound III·Et2O gradually loses solvate molecules to be converted to the complex [CuL3(POP)]BF4 (III). According to single-crystal X-ray diffraction data, the complexes (I, II, III·Et2O) are ionic; the copper atom in the [CuLn(POP)]+ cation is located in a distorted tetrahedral environment (CuN2P2). The photoluminescence properties of the obtained complexes (I–III) were studied in the solid state and in solution. In the absorption spectra of the complexes, a charge transfer band is observed at 380–385 nm; excitation in this range gives rise to two emission bands at 480 and 650 nm in solution. In the solid state, the complexes show photoluminescence only in the red range (λmax = 600–610 nm) with microsecond lifetimes. It was Found that complexes I and III with a more regular tetrahedral environment have quantum yields an order of magnitude higher than the quantum yield observd for complex II.

KW - 1,10-phenanthroline

KW - copper(I)

KW - crystal structure

KW - fluorescence

KW - heteroleptic coordination compounds

KW - phosphorescence

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85208981356&origin=inward&txGid=11befc4c24e06dda7ee100ce47fdcb72

UR - https://www.mendeley.com/catalogue/0e8aeea6-1fdd-3e98-9605-7a0904526d1b/

U2 - 10.1134/S1070328424600657

DO - 10.1134/S1070328424600657

M3 - Article

VL - 50

SP - 567

EP - 578

JO - Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya

JF - Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya

SN - 1070-3284

IS - 8

ER -