Novel mercury selenidoantimonates with structures ranging from one-dimensional ribbon to three-dimensional open-framework.

With a transition metal (TM) complex or a protonated organic amine as a structure-directing agent (SDA), five novel Hg-Sb-Se compounds with the architectures ranging from one-dimensional (1D) ribbon, two-dimensional (2D) layer, to three-dimensional (3D) open-framework have been solvothermally synthesized and structurally characterized. The compounds [Ni(1,2-pda)3]HgSb2Se5 (1) (1,2-pda = 1,2-diaminopropane) and [Mn(dien)2]HgSb2Se5 (2) (dien = diethylenetriamine) feature a 1D-[HgSb2Se5]n(2n-) ribbon assembled by the {HgSb2Se5} groups. The compounds [Ni(en)3]Hg2Sb2Se6 (3) (en = ethylenediamine) and [Ni(en)(teta)]Hg2Sb2Se6 (4) (teta = triethylenetetramine) feature a 2D-[Hg2Sb2Se6]n(2n-) layer constructed by the combination of the {HgSbSe3}n ribbons. The compound [(Me)2NH2][Hg3Sb3Se8] (5) contains the dimeric {Sb2Se5} groups and {Hg3SbSe7}n layers, which are interconnected into a 3D-[Hg3Sb3Se8]n(n-) anionic framework with [(Me)2NH2](+) ions located in the channels. Furthermore, the comparison between 2 and recently reported [Mn(tren)]HgSb2Se5 based on the optical diffuse-reflectance measurements and band structure calculations indicates that the Mn(2+) ions with different coordination environments make distinct contributions to the CBM of the band structure.