The synthesis of new molybdenum cluster selenocyanide anionic complexes [Mo6Se8(CN)6]7- and [Mo6Se8(CN)6]6- is reported. The [Mo6Se8(CN)6]7- ion was obtained by excision of the cluster core [Mo6Se8] from a Chevrel phase in the reaction of Mo6Se8 with KCN at 650 degrees C; the [Mo6Se8(CN)6]6- ion is formed by oxidation of [Mo6Se8(CN)6]7-. New cluster salts K7[Mo6Se8(CN)6] x 8H2O (1) and (Me4N)4K2[Mo6Se8(CN)6] x 10H2O (2) were isolated and their crystal structures were solved. Compound 1 crystallizes in the cubic space group Fm3m (a=15.552(2) A, Z=4, V=3761.5(8) A3), compound 2 crystallizes in the triclinic space group P1 (a=11.706(2), b=11.749(2), c=12.459(2) A, alpha=72.25(1), beta=77.51(1), gamma=63.04(1), Z=1, V=1448.5(4) A3). Compound 1 is paramagnetic due to an availability of 21 electrons per Mo6 cluster; cyclic voltammetry reveals a quasi-reversible transition [Mo6Se8(CN)6]7- <--> [Mo6Se8(CN)6]6-, E1/2=0.63 V.
2000 luminescence, fluorescence luminescence, fluorescence (solids and liquids) D 6540
-006Unusual Capping Chalcogenide Dependence of the Luminescence Quantum Yield of the Hexarhenium(III) Cyano Complexes [Re 6 (µ 3 -E) 8 (CN) 6 ] 4− , E 2− : Se 2− ¿ S 2− ¿ Te 2− .-The [Re 6 (µ 3 -E) 8 (CN) 6 ] 4− clusters with E: S, Se, and Te are luminescent at room temperature. The emission quantum yields and lifetimes decrease in the order Se ¿ S ¿¿ Te.
Two novel octahedral rhenium(III) selenocyanide cluster complexes [(nBu) 4 N] 2 Ni(H 2 O) 5 [Re 6 Se 8 (CN) 6 ]·2H 2 O (1) and [(nBu) 4 N] 2 Mn(H 2 O) 4 [Re 6 Se 8 (CN) 6 ]·2H 2 O (2) have been prepared by the reaction of K 4 [Re 6 Se 8 (CN) 6 ]·3.5H 2 O, (nBu) 4 NBr and Ni(OAc) 2 (or MnSO 4 ) in aqueous solution. The complexes have been structurally solved in the orthorhombic unit cell Pbca with parameters: a = 19.393(2), b = 17.292(2), c = 37.255(4) Å for 1, and a = 19.518(4), b = 17.488(3), c = 37.997(5) Å for 2. The cluster anions and M 2+ form ionic pairs
Netze mit Clustern als Spacern: Chirale, heterometallische Koordinationspolymere (siehe Bild) können gezielt durch Kombination des chiralen (2S,3S)‐1,2,3,4‐Tetraaminobutan‐Liganden mit einem labilen zweiwertigen Übergangsmetallkation wie Cu2+ und einem mehrkernigen Rhenium‐Chalkogenid‐Cyano‐Cluster erhalten werden.
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