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

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 ArticleGenre_short.SHORT_COMMUNICATION

Journal

Inorganic Chemistry Communications
ISSN: 1387-7003 , E-ISSN: 1879-0259

Output data

Year: 2025, Volume: 174, Pages: 114048 Pages count : 8 DOI: 10.1016/j.inoche.2025.114048

Authors

Skvortsova Sofia V. ^1,2 , Shekhovtsov Nikita A. ¹ , Rakhmanova Marianna I. ¹ , Samsonenko Denis G. ¹ , Nikolaenkova Elena B. ³ , Bushuev Mark B. ¹

Affiliations

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3, Acad. Lavrentiev Ave., Novosibirsk 630090, Russi
2	Novosibirsk State University, 2, Pirogova Ave., Novosibirsk 630090, Russia
3	N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of Russian Academy of Sciences, 9, Acad. Lavrentiev Ave., Novosibirsk 630090, Russia

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 %.

Skvortsova S.V. , Shekhovtsov N.A. , Rakhmanova M.I. , Samsonenko D.G. , Nikolaenkova E.B. , Bushuev M.B.
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
Inorganic Chemistry Communications. 2025. V.174. P.114048. DOI: 10.1016/j.inoche.2025.114048 WOS OpenAlex

Submitted:	Nov 26, 2024
Accepted:	Feb 2, 2025
Published online:	Feb 4, 2025
Published print:	Apr 1, 2025

Web of science:	WOS:001426328000001
OpenAlex:	W4407116228

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