Review. Synthesis of Inorganic-Organic Hybrid Thiometallate Materials with a Special Focus on Thioantimonates and Thiostannates and in situ X-Ray Scattering Studies of their Formation

Abstract

A rich variety of inorganic-organic hybrid thioantimonates and thiostannates were prepared during the last few years under solvothermal conditions applying organic amine molecules or transition metal complexes as structure directors. In this review synthetic approaches to and structural features of these thiometallates are discussed. For thioantimonates(III) the structures range from well isolated thioanions to three-dimensional networks, whereas the structural chemistry of thiostannates(IV) is strongly dominated by the [Sn 2 S 6 ] 4− anion, and no three-dimensional thiostannate has been reported so far. In the structures of thioantimonates(III) several primary building units like the [SbS 3 ] trigonal pyramid, the [SbS 4 ] unit or even the [SbS 5 ] moiety are joined by vertex-and/or edge-linkages to form building blocks of higher structural hierarchy like [Sb 3 S 4 ] semi-cubes or Sb x S x heterocycles. A pronounced difference between thioantimonate and thiostannate chemistry is the tendency of Sb(III) to enhance the coordination geometry via so-called secondary bonds. In most cases the environment of Sb(III) is better described as a 3 + n polyhedron with n = 1 -3. The thioantimonate(V) structural chemistry is less rich than that of thioantimonates(III), and the [SbS 4 ] 3− anion shows no tendency for further condensation. By applying suitable multidentate amine molecules, transition metal cations which normally prefer bonding to the N atoms of the amines can be incorporated into the thiometallate frameworks.

Chalcogenidoantimonates by Solvothermal Synthesis in Liquid Ammonia

“…These entire characteristics lead to a large structural variability of chalcogenidoantimonates(III), which today represent a widely explored class of compounds showing a rich structural chemistry and interesting physical properties. [1][2][3] Initially investigated by Schäfer, [4][5][6][7] thio-and in somewhat lesser extent selenidoantimonates(III) are in the focus of research interests of many scientific groups. Outstanding contributions originate from the groups of Parise, [8][9][10] Powell, [11][12][13] and Bensch.…”

“…[1,2] We have recently shown that the solvothermal treatment of the less-noble metals manganese, iron, and zinc with elemental chalcogens in liquefied ammonia or methylamine leads to polychalcogenides [32][33][34] and trichalcogenidotellurates(IV) [35] with the metals converted into the respective cationic complexes bearing ammine or methylamine ligands. The reactions can be carried out under remarkable mild condi-ner-connected trigonal-pyramidal SbS 3 and SbSe 3 are the characteristic building units. 1 and 4 contain 2D polymeric anions, in the latter case with Zn 2+ cations incorporated in a selenidoantimonate(III) network.…”

“…The polymeric anion in the structure of 3 is a helical chain. 2 is a molecular compound and contains dinuclear anions [S 3 Sb-S-Zn(NH 3 tions under autogenous pressure with gentle heating to 50°C or even at room temperature. We expanded this low-temperature solvothermal synthetic procedure in liquid ammonia to mixtures of the metals zinc and manganese, the chalcogens sulfur and selenium, and antimony and succeeded in the preparation and characterization of two thioantimonate and two selenidoantimonates, namely [Zn(NH 3 …”

New Thiostannates Synthesized Under Solvothermal Conditions: Crystal Structures of (trenH)2Sn3S7 and {[Mn(tren)]2Sn2S6}

“…[Sn 4 S 9 ] 2− ) with Sn 3 S 4 semi-cubes as main structural motifs. These well-known thiostannate families feature many members, and several interesting experiments were done with outstanding results [12]. In the meantime, a relatively large number of thiostannates have been synthesized under solvothermal conditions applying different structure-directing agents [13 -19].…”

Solvothermal Syntheses and Crystal Structures of New One-dimensional Selenogallates [bappH2][Ga2Se4] (bapp = 1,4-Bis-(3-aminopropyl)piperazine) and [Mn(en)3][Ga2Se5] (en = Ethylenediamine)

“…Solvothermal synthesis is the most efficient method for the preparation of metal chalcogeno (chalcogenido) frameworks of main group elements templated 0932-0776 / 11 / 0900-0877 $ 06.00 c 2011 Verlag der Zeitschrift für Naturforschung, Tübingen · http://znaturforsch.com by organo-ammonium or metal cations as counterions [13,14]. Meanwhile, organic amines with different C/N ratios and molecular structures play a key role in the formation of various architectures.…”