Mixed-Valent Selenidoantimonates(III,V) with Transition-Metal Complexes as Counterions: Solvothermal Syntheses and Characterization of [M(dien)<sub>2</sub>]<sub>2</sub>Sb<sub>4</sub>Se<sub>9</sub> (M = Mn, Fe), [Co(dien)<sub>2</sub>]<sub>2</sub>Sb<sub>2</sub>Se<sub>6</sub>, and [Ni(dien)<sub>2</su
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Novel selenidoantimonate compounds [M(dien)2]2Sb4Se9 [M = Mn (1), Fe (2)], [Co(dien)2]2Sb2Se6 (3), and [Ni(dien)2]2Sb2Se5 (4) (dien = diethylenetriamine) were solvothermally synthesized and characterized. The unique features of compounds 1−3 are the mixed-valent anionic structures constructed by the SbIIISe3 trigonal pyramid and SbVSe4 tetrahedron. Three SbIIISe3 pyramids share common corners, forming a heterocyclic Sb3Se6 moiety, and the Sb3Se6 moieties are further connected with SbVSe4 tetrahedra to form the novel one-dimensional [Sb4Se94-]n anionic chain in 1 and 2. The discrete [Sb2Se6]4- anion in 3 is formed by an SbIIISe3 trigonal pyramid and an SbVSe4 tetrahedron sharing a common corner. The [Sb2Se5]4- anion in 4 is composed of two SbIIISe3 trigonal pyramids connected in the same manner as the [Sb2Se6]4- anion. The mixed-valent [Sb4Se94-]n and [Sb2Se6]4- anions were not observed before. The synthesis and solid-state structural studies of the title compounds show that the transition-metal complexes exhibit different structure-directing effects on the formation of selenidoantimonates in dien. Extensive N−H···Se hydrogen bonds are observed between cations and anions in compounds 1−4, resulting in three-dimensional network structures. Optical and thermal properties of the compounds are reported.
