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

Abstract

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

Evidences of the non-stoichiometry and control of the composition of the cluster-based solid solution K6[Re6-xMoxS8(CN)5] (x=2.75–3.63)

“…Formation of non-stoichiometric phases is quite rare in the chemistry of clusters. Heterometallic clusters represent a special type of cluster compounds containing different metal atoms within the core [13][14][15][16][17][18][19][20][21][22][23] . The introduction of another metal atom makes it possible to change the properties of cluster compounds in a controlled manner, and can also lead to interesting optical properties due to a decrease of the symmetry of the cluster core.…”

Heterometallic clusters with a new {Re3Mo3S8} core: direct synthesis, properties and DFT calculations

“…[4][5][6][7][8] The described scheme has been successfully applied in the synthesis of heterometallic {M 6 Q 8 }-type clusters with {Re 5 Os}, {Re 4 Os 2 } and {Re 3 Os 3 } cores. [9][10][11][12] The only known soluble heterometallic cluster with a {Re 6Àn Mo n Q 8 } core is Cs 5 [Re 6Àx Mo x S 8 (CN) 6 ]Á 2H 2 O (x = 1.5-1.8). 13 It was prepared by the rearrangement of the tetranuclear cluster Re 3 MoS 4 Te 4 in molten KCN and contained two clusters with different cores: {Re 5 MoS 8 } + with 24 cluster valence electrons (CVE) and {Re 4 Mo 2 S 8 } + with 23 CVE.…”