Mild solvothermal syntheses and characterization of layered copper thioantimonates(III) and thioarsenate(III).

The new copper thioantimonates(III) and thioarsenate(III) Rb2Cu2Sb2S5 (1), Cs2Cu2Sb2S5 (2), and Rb8Cu6As8S19 (3) have been synthesized solvothermally. Compound 1 contains a [Cu2SbS3] net to which [Sb2S4] chains adhere through Cu-S bonds and Sb-Cu interactions to give a layered structure. In compound 2, the layer is formed by edge-sharing tetrahedral CuS4 chains linked by dimeric [Sb2S5] units. The layered structure in compound 3 is constructed by helical chains built from [Cu3S7] moieties and dimeric [As2S5] units which are further connected by tetrameric [As4S9] groups. Their optical and thermal properties have been investigated.

Copper-rich framework sulfides: A(4)Cu(8)Ge(3)S(12) (A = K, Rb) with cubic perovskite structure.

Two copper-rich open-framework sulfides, K(4)Cu(8)Ge(3)S(12) (1) and Rb(4)Cu(8)Ge(3)S(12) (2), have been synthesized under solvothermal conditions. Compounds 1 and 2 are isostructural and contain icosahedral [Cu(8)S(12)](16-) clusters as basic building blocks. These clusters are primitive cubic packed and connect to one another by discrete Ge(4+) ions to generate 3D copper-rich Cu-Ge-S framework and form 3D channels along 100 directions where the alkali metal cations reside. These two open-framework sulfides crystallize in cubic perovskite structure.

(H(2)en)(2)Cu(8)Sn(3)S(12): a trigonal CuS(3)-based open-framework sulfide with interesting ion-exchange properties.

(H(2)en)(2)Cu(8)Sn(3)S(12) contains a trigonal CuS(3)-based framework into which Sn(4+) ions are incorporated, and exhibits multiple channel systems and interesting ion-exchange properties.

Syntheses and characterization of a series of silver-thioantimonates(III) and thioarsenates(III) containing two types of silver-sulfur chains.

Three framework silver-thioantimonates, K(3)Ag(9)Sb(4)S(12)(1), Rb(3)Ag(9)Sb(4)S(12)(2), and Cs(3)Ag(9)Sb(4)S(12)(3), and one layered silver-thioarsenate, CsAg(2)AsS(3)(4), have been synthesized solvothermally in the presence of thiophenol as a mineralizer. Compounds 1, 2, and 3 are isostructural and contain infinite silver-sulfur chains [Ag(9)S(12)](15-). These chains are connected to one another by the antimony atoms to generate wide channels along the [001] direction where the alkali metal cations reside. The structure of 4 consists of helical chains [Ag(2)S(3)](4-) linked by the arsenic atoms to form layers with potassium ions between the layers.

New framework iodoargentates: M(en)3Ag2I4 (M=Zn, Ni) with tridymite topology.

Two novel framework compounds, Zn(en) 3Ag2I4 (1) and Ni(en) 3Ag2I4 (2), have been synthesized by a self-assembly reaction. Both of them contain an unexpected framework, Ag2I4(2-) with tridymite topology, and the discrete M(en)3(2+) cations are located in the channels. Their thermal properties and circular dichroism spectra were investigated.