biostudies-literatureYakovlev GBRussian Science Foundation1189https://www.ebi.ac.uk/biostudies/studies/S-EPMC9920877biostudies-literatureUnknown28(3)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 (<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 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.Molecules (Basel, Switzerland)Tetranuclear Copper(I) and Silver(I) Pyrazolate Adducts with 1,1'-Dimethyl-2,2'-bibenzimidazole: Influence of Structure on Photophysics.PMC992087722-73-10130Chernyadyev AYShubina ESFilippov OAYakovlev GBTitov AASmol'yakov AFfalseTetranuclear 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]₃, 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 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.2023-01-01T00:00:00Z2023 Jan2025-04-22T11:59:36.519Z2024-11-09T13:04:03.596ZS-EPMC99208773677085510.3390/molecules28031189