Luminescent zinc(II) complexes and ionic solids on the base of a 2-(1H-pyrazol-1-yl)-4-(2-hydroxyphenyl)pyrimidine ligand: switching proton transfer off by complexation and protonation

Luminescent zinc(II) complexes and ionic solids on the base of a 2-(1H-pyrazol-1-yl)-4-(2-hydroxyphenyl)pyrimidine ligand: switching proton transfer off by complexation and protonation Full article

Journal

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

Output data

Year: 2025, Volume: 182, Article number : 115461, Pages count : 9 DOI: 10.1016/j.inoche.2025.115461

Tags

Zinc(II) complexes, Pyrazolyl pyrimidine ligand, X-ray structure, Luminescence, DFT calculations

Authors

Shekhovtsov Nikita A. ¹ , Vorobyeva Sofia N. ¹ , Sukhikh Taisiya S. ¹ , Ryadun Alexey A. ¹ , Nikolaenkova Elena B. ² , Tikhonov Alexey Y. ² , Bushuev Mark B. ¹

Affiliations

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

Dinuclear zinc(II) complexes [Zn2L2X2]·nSolv (X = Cl, nSolv = 1.5MeOH; X = Br, I, nSolv = CH2Cl2·0.5MeOH) and ionic solids [H2L]X·H2O (X = Cl, Br) on the base of 2-(3,5-dimethyl-1H-pyrazol-1-yl)-4-(2-hydroxyphenyl)pyrimidine (HL) were synthesized. In these compounds, excited state intramolecular proton transfer in the ligand core is switched off as a result of complexation and protonation. In the structure of zinc(II) complexes, mononuclear {ZnLX} units are combined into non-centrosymmetric dinuclear [Zn2L2X2] molecules due to the bridging function of the deprotonated hydroxyphenyl group. The crystal structures of [H2L]X·H2O are stabilized by the formation of supramolecular clusters with N–H⋅⋅⋅O and O–H⋅⋅⋅Cl hydrogen bonds between [H2L]+ cations, H2O molecules and X− anions. Whereas the ionic compounds with the protonated ligand, [H2L]X·H2O, exhibit only weak fluorescence in the blue region, the zinc(II) complexes, [Zn2L2X2]·nSolv, demonstrate bright fluorescence in the green region whose efficiency increases with a decrease in the size of the halogen atom (PLQY 7 %, 10 % and 21 % for X = I, Br and Cl, respectively), reflecting reduced non-radiative decay through triplet-state quenching as the heavy atom effect weakens.

Shekhovtsov N.A. , Vorobyeva S.N. , Sukhikh T.S. , Ryadun A.A. , Nikolaenkova E.B. , Tikhonov A.Y. , Bushuev M.B.
Luminescent zinc(II) complexes and ionic solids on the base of a 2-(1H-pyrazol-1-yl)-4-(2-hydroxyphenyl)pyrimidine ligand: switching proton transfer off by complexation and protonation
Inorganic Chemistry Communications. 2025. V.182. 115461 :1-9. DOI: 10.1016/j.inoche.2025.115461

Submitted:	Jun 27, 2025
Accepted:	Sep 4, 2025
Published online:	Sep 5, 2025
Published print:	Dec 1, 2025

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