Tetranuclear Copper(I) and Silver(I) Pyrazolate Adducts with 1,1′-Dimethyl-2,2’-bibenzimidazole: Influence of Structure on Photophysics
A reaction of a cyclic trinuclear copper(I) or silver(I) pyrazolate complex ([MPz]<sub>3</sub>, M = Cu, Ag) with 1,1′-dimethyl-2,2’-bibenzimidazole (<b>L</b>) leads to the formation of tetranuclear adducts decorated by one or two molecules of a diimine ligand, depending on th...
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MDPI AG
2023-01-01
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| author | Gleb B. Yakovlev Aleksei A. Titov Alexander F. Smol’yakov Andrey Yu. Chernyadyev Oleg A. Filippov Elena S. Shubina |
| author_facet | Gleb B. Yakovlev Aleksei A. Titov Alexander F. Smol’yakov Andrey Yu. Chernyadyev Oleg A. Filippov Elena S. Shubina |
| author_sort | Gleb B. Yakovlev |
| collection | DOAJ |
| description | A reaction of a cyclic trinuclear copper(I) or silver(I) pyrazolate complex ([MPz]<sub>3</sub>, M = Cu, Ag) with 1,1′-dimethyl-2,2’-bibenzimidazole (<b>L</b>) 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 <b>L</b> 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 M<sub>4</sub> 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 Ag<sub>4</sub>Pz<sub>4</sub>L exhibited dual emission from both the singlet and triplet states, even at room temperature. |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T09:33:24Z |
| publishDate | 2023-01-01 |
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| series | Molecules |
| spelling | doaj.art-6cdca60d2fba4012bf4eac67d7c98d6c2023-11-16T17:28:53ZengMDPI AGMolecules1420-30492023-01-01283118910.3390/molecules28031189Tetranuclear Copper(I) and Silver(I) Pyrazolate Adducts with 1,1′-Dimethyl-2,2’-bibenzimidazole: Influence of Structure on PhotophysicsGleb B. Yakovlev0Aleksei A. Titov1Alexander F. Smol’yakov2Andrey Yu. Chernyadyev3Oleg A. Filippov4Elena S. Shubina5A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str., 28, 119334 Moscow, RussiaA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str., 28, 119334 Moscow, RussiaA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str., 28, 119334 Moscow, RussiaA. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky prosp. 31/4, 199071 Moscow, RussiaA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str., 28, 119334 Moscow, RussiaA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str., 28, 119334 Moscow, RussiaA reaction of a cyclic trinuclear copper(I) or silver(I) pyrazolate complex ([MPz]<sub>3</sub>, M = Cu, Ag) with 1,1′-dimethyl-2,2’-bibenzimidazole (<b>L</b>) 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 <b>L</b> 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 M<sub>4</sub> 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 Ag<sub>4</sub>Pz<sub>4</sub>L exhibited dual emission from both the singlet and triplet states, even at room temperature.https://www.mdpi.com/1420-3049/28/3/1189cyclic trinuclear complexpyrazolate adductscopper(I)silver(I)TD-DFTphotoluminescence |
| spellingShingle | Gleb B. Yakovlev Aleksei A. Titov Alexander F. Smol’yakov Andrey Yu. Chernyadyev Oleg A. Filippov Elena S. Shubina Tetranuclear Copper(I) and Silver(I) Pyrazolate Adducts with 1,1′-Dimethyl-2,2’-bibenzimidazole: Influence of Structure on Photophysics Molecules cyclic trinuclear complex pyrazolate adducts copper(I) silver(I) TD-DFT photoluminescence |
| title | Tetranuclear Copper(I) and Silver(I) Pyrazolate Adducts with 1,1′-Dimethyl-2,2’-bibenzimidazole: Influence of Structure on Photophysics |
| title_full | Tetranuclear Copper(I) and Silver(I) Pyrazolate Adducts with 1,1′-Dimethyl-2,2’-bibenzimidazole: Influence of Structure on Photophysics |
| title_fullStr | Tetranuclear Copper(I) and Silver(I) Pyrazolate Adducts with 1,1′-Dimethyl-2,2’-bibenzimidazole: Influence of Structure on Photophysics |
| title_full_unstemmed | Tetranuclear Copper(I) and Silver(I) Pyrazolate Adducts with 1,1′-Dimethyl-2,2’-bibenzimidazole: Influence of Structure on Photophysics |
| title_short | Tetranuclear Copper(I) and Silver(I) Pyrazolate Adducts with 1,1′-Dimethyl-2,2’-bibenzimidazole: Influence of Structure on Photophysics |
| title_sort | tetranuclear copper i and silver i pyrazolate adducts with 1 1 dimethyl 2 2 bibenzimidazole influence of structure on photophysics |
| topic | cyclic trinuclear complex pyrazolate adducts copper(I) silver(I) TD-DFT photoluminescence |
| url | https://www.mdpi.com/1420-3049/28/3/1189 |
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