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Octahedral cyanohydroxo cluster complex trans-[Re6Se8(CN)4(OH)2]: Synthesis, crystal structure, and properties |
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| Authors: | Yuri V Mironov Konstantin A Brylev Sung-Jin Kim Svetlana G Kozlova Vladimir E Fedorov |
| Institution: | a Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 Acad. Lavrentiev Prosp., 630090 Novosibirsk, Russia b Ewha Womans University, 11-1 Daehyun-dong, Seodaemun-gu, 120-750 Seoul, Republic of Korea c Department of Chemistry, Graduate School of Science, Hokkaido University, 060-0810 Sapporo, Japan |
| Abstract: | A hexarhenium cyanohydroxo anionic cluster complex Re6Se8(CN)4(OH)2]4− was synthesized for the first time starting from Re6Se8(OH)6]4−, which was crystallized as a salt of the composition Cs2.75K1.25Re6Se8(CN)4(OH)2]·H2O (1). The reaction of the complex with Cu2+ in an aqueous ammonia or methylamine solutions afforded Cu(NH3)5]2Re6Se8(CN)4(OH)2]·8H2O (2) or {Cu(CH3NH2)4}2Re6Se8(CN)4(OH)2] (3), respectively. All of these three compounds were characterized by a single-crystal X-ray diffraction method. Compound 1 is crystallized in the tetragonal space group I4/m with eight formula units per cell (a = b = 17.4823(14) Å, c = 19.430(2) Å, V = 5938.3(10) Å3); compound 2 is crystallized in the monoclinic space group P21/n with two formula units per cell (a = 12.1845(13) Å, b = 8.6554(9) Å, c = 19.2568(19) Å, β = 91.081(2)°, V = 2030.5(4) Å3); compound 3 is crystallized in the orthorhombic space group Cmcm with four formula units per cell (a = 19.816(4) Å, b = 14.611(3) Å, c = 13.751(3) Å, V = 3981.2(13) Å3). The luminescence properties of 1 were studied in both aqueous solution and solid state. In addition, the electronic structure of Re6Se8(CN)4(OH)2]4− was elucidated by DFT calculations. |
| Keywords: | Cluster compounds Rhenium Luminescence Crystal structure Electronic structure |
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