Octahedral cyanohydroxo cluster complex trans-[Re6Se 8(CN)4(OH)2]4-: Synthesis, crystal structure, and properties

Abstract

A hexarhenium cyanohydroxo anionic cluster complex [Re6Se 8(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 Cs 2.75K1.25[Re6Se8(CN) 4(OH)2]·H2O (1). The reaction of the complex with Cu2+ in an aqueous ammonia or methylamine solutions afforded [Cu(NH3)5]2[Re6Se 8(CN)4(OH)2]·8H2O (2) or [{Cu(CH3NH2)4}2Re6Se 8(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) , c = 19.430(2) , V = 5938.3(10) 3); compound 2 is crystallized in the monoclinic space group P2 1/n with two formula units per cell (a = 12.1845(13) , b = 8.6554(9) , c = 19.2568(19) , β = 91.081(2)°, V = 2030.5(4) 3); compound 3 is crystallized in the orthorhombic space group Cmcm with four formula units per cell (a = 19.816(4) , b = 14.611(3) , c = 13.751(3) , V = 3981.2(13) 3). 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. © 2011 Elsevier Ltd. All rights reserved.