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Tetranuclear Copper(I) and Silver(I) Pyrazolate Adducts with 1,1'-Dimethyl-2,2’-bibenzimidazole: Influence of Structure on Photophysicsстатья
- Авторы: Yakovlev Gleb B., Titov Aleksei A., Smol’yakov Alexander F., Chernyadyev Andrey Yu, Filippov Oleg A., Shubina Elena S.
- Журнал: Molecules
- Том: 28
- Номер: 3
- Год издания: 2023
- Издательство: MDPI
- Местоположение издательства: Basel, Switzerland
- Номер статьи: 1189
- DOI: 10.3390/molecules28031189
- Аннотация: A reaction of a cyclic trinuclear copper(I) or silver(I) pyrazolate complex ([MPz]3, M = Cu, Ag) with 1,1′-dimethyl-2,2’-bibenzimidazole (L) leads to the formation of tetranuclear adducts decorated by one or two molecules of a diimine ligand, depending on the amount of the ligand added (0.75 or 1.5 equivalents). The coordination of two L molecules stabilizes the formation of a practically idealized tetrahedral four-metal core in the case of a copper-containing complex and a distorted tetrahedron in the case of a Ag analog. In contrast, complexes containing one molecule of diimine possess two types of metals, two- and three-coordinated, forming the significantly distorted central M4 cores. The diimine ligands are twisted in these complexes with dihedral angles of ca. 50–60°. A TD-DFT analysis demonstrated the preference of a triplet state for the twisted 1,1′-dimethyl-2,2’-bibenzimidazole and a singlet state for the planar geometry. All obtained complexes demonstrated, in a solution, the blue fluorescence of the ligand-centered (LC) nature typical for free diimine. In contrast, a temperature decrease to 77 K stabilized the structure close to that observed in the solid state and activated the triplet states, leading to green phosphorescence at ca. 500 nm. The silver-containing complex Ag4Pz4L exhibited dual emission from both the singlet and triplet states, even at room temperature.
- Добавил в систему: Астахов Григорий Сергеевич
Прикрепленные файлы
| № | Имя | Описание | Имя файла | Размер | Добавлен |
|---|---|---|---|---|---|
| 1. | Полный текст | molecules-28-01189.pdf | 1,1 МБ | 30 января 2023 [AstakhovGS] |