Synthesis and structures of new octahedral heterometal rhenium-osmium cluster complexes

Abstract

New octahedral anionic heterometal rhenium-osmium cluster complexes [Re 5OsSe 8(OH) 6] 3- and [Re 4Os 2Se 8(OH) 6] 2- were synthesized starting from [Re 5OsSe 8Cl 6] 3- and [Re 4Os 2Se 8Cl 6] 2-, respectively. They were isolated as salts of the compositions Cs 3[Re 5OsSe 8(OH) 6] · 11H 2O (I), K 3[Re 5OsSe 8(OH) 6] · 7H 2O (II), and K 2[Re 4Os 2Se 8(OH) 6] · 3H 2O (III). The protonation of the terminal OH ligands of [Re 5OsSe 8(OH) 6] 3- in an aqueous solution resulted in crystallization of a neutral complex [Re 5OsSe 8(H 2O) 3(OH) 3] · 12H 2O (IV). The compounds have been characterized by single-crystal X-ray diffraction analysis. The luminescence properties of [Re 5OsSe 8(OH) 6] 3- and [Re 4Os 2Se 8(OH) 6] 2- were studied. In addition, the electronic structures of the complexes were elucidated by DFT calculations. © Pleiades Publishing, Ltd., 2012.