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Copper(I) complexes with a 4-(1H-pyrazol-1-yl)-2-(pyridin-2-yl)pyrimidine ligand: Synthesis, structures and theoretical insights into the tuning of emission properties. / Skvortsova, Sofia V.; Shekhovtsov, Nikita A.; Rakhmanova, Marianna I. и др.
в: Inorganic Chemistry Communications, Том 174, 114048, 04.2025.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Copper(I) complexes with a 4-(1H-pyrazol-1-yl)-2-(pyridin-2-yl)pyrimidine ligand: Synthesis, structures and theoretical insights into the tuning of emission properties
AU - Skvortsova, Sofia V.
AU - Shekhovtsov, Nikita A.
AU - Rakhmanova, Marianna I.
AU - Samsonenko, Denis G.
AU - Nikolaenkova, Elena B.
AU - Bushuev, Mark B.
N1 - The research was supported by the Ministry of Science and Higher Education of the Russian Federation (Nikolaev Institute of Inorganic Chemistry SB RAS, project number 121031700321-3; N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry)
PY - 2025/4
Y1 - 2025/4
N2 - A series of mononuclear copper(I) complexes, [CuL(PPh3)Br], [CuL(PPh3)I] and [CuL(PPh3)2](PF6) (L = 4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-(pyridin-2-yl)pyrimidine), was synthesized. Free L exhibits bright fluorescence in the blue region (PLQY 29 %). The complexes demonstrate luminescence in the yellow-to-red region. Considerable emission quenching in [CuL(PPh3)Br] and [CuL(PPh3)I] (PLQY < 1 %) is contributed by the electron-poor heterocycles in the ligand structure, which favour the overstabilization of LUMO in the T1 state, the decrease of HOMO-LUMO and S0-T1 gaps and, as a consequence, the increase of the ratio of non-radiative events. Instead, the introduction of the second PPh3 molecule in the coordination sphere of Cu+ ion on going from [CuL(PPh3)Br] and [CuL(PPh3)I] to [CuL(PPh3)2](PF6) causes the widening of the HOMO-LUMO and S0-T1 gaps, which in turn leads to the increase of PLQY up to 9 %.
AB - A series of mononuclear copper(I) complexes, [CuL(PPh3)Br], [CuL(PPh3)I] and [CuL(PPh3)2](PF6) (L = 4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-(pyridin-2-yl)pyrimidine), was synthesized. Free L exhibits bright fluorescence in the blue region (PLQY 29 %). The complexes demonstrate luminescence in the yellow-to-red region. Considerable emission quenching in [CuL(PPh3)Br] and [CuL(PPh3)I] (PLQY < 1 %) is contributed by the electron-poor heterocycles in the ligand structure, which favour the overstabilization of LUMO in the T1 state, the decrease of HOMO-LUMO and S0-T1 gaps and, as a consequence, the increase of the ratio of non-radiative events. Instead, the introduction of the second PPh3 molecule in the coordination sphere of Cu+ ion on going from [CuL(PPh3)Br] and [CuL(PPh3)I] to [CuL(PPh3)2](PF6) causes the widening of the HOMO-LUMO and S0-T1 gaps, which in turn leads to the increase of PLQY up to 9 %.
KW - Copper(I) complexes
KW - DFT calculations
KW - Luminescence
KW - Pyrazolyl pyridinyl pyrimidine ligand
KW - X-ray structure
UR - https://www.mendeley.com/catalogue/63e7c3ee-6a60-3f67-bddf-d9375572f12f/
UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85217057708&origin=inward&txGid=ccf713e4bb1a693adbde16843d252a70
U2 - 10.1016/j.inoche.2025.114048
DO - 10.1016/j.inoche.2025.114048
M3 - Article
VL - 174
JO - Inorganic Chemistry Communication
JF - Inorganic Chemistry Communication
SN - 1387-7003
M1 - 114048
ER -
ID: 64692630