Ion pair charge-transfer thiogermanate salts [MV]2Ge4S10·xSol: solvent induced crystal transformation and photocurrent responsive properties.

As most of the chalcogenidometalate anions are well-known electron-rich systems, design and preparation of ion pair compounds, by integrating an organic acceptor (A) with an inorganic chalcogenidometalate donor (D), are an attractive strategy to obtain new functional materials. We report herein the single-crystal structures and properties of three new ion pair charge-transfer (IPCT) compounds by incorporating thiogermanates with methylviologen (MV(2+), N,N'-dimethyl-4,4'-bipyridinium dication), [MV]2Ge4S10·xSol (Sol = solvent). Sharp and fast solvent-induced color changes and switchable fluorescence emission are observed for the compounds.

3-D germanate constructed with Ge7 cluster layers and nickel-ethanolamine linkage.

A Ge(7) germanate, [Ni(H(2)O)(μ-C(2)H(6)NO)(2)Ge(7)O(14)(C(2)H(7)NO)]·C(2)H(5)OH (1), was prepared by the solvothermal method using ethanolamine (C(2)H(7)NO) as solvent, ligand, and structure-directing agent. Compound 1 shows an unusual GeO framework fused with transition metal complex. The 2-D layers of Ge(7) clusters are linked by a [Ni(H(2)O)(μ-C(2)H(6)NO)(2)] moiety, forming a 3-D architecture.

Ionic crystals of {[Ni(phen)3]2Ge4S10}·xSol, showing solid-state solvatochromism and rapid solvent-induced recrystallization.

Thiogermanates, {[Ni(phen)(3)](2)Ge(4)S(10)}·xSol (Sol = 4MeOH·12H(2)O (1) and 24H(2)O (2)) were prepared and characterized by single-crystal structure analysis. There are large quantities of the solvent molecules that cocrystallize with the anions and cations and form a strong hydrogen bonding network (O-H···S and O···H-O-H···O). Reversible yellow-pink color change with fast speed was found for these compounds, when the crystals were immersed in alcohol solvents and water alternately.

1-D Selenidoindates {[In2Se5]}∞ directed by chiral metal complex cations of 1,10-phenanthroline.

Two 1-D selenidoindates {[M(phen)(3)]In(2)Se(5)·H(2)O}(n) (M = Ni, Fe) were synthesized by a solvothermal method. The 1-D {[In(2)Se(5)](2-)}(n) anion is a new type of single 1-D structure constituted by an alternately fused four-membered In(2)Se(2) ring and five-membered In(2)Se(3) ring. The chalcogenoindates were separated as mechanical racemic mixtures of single enantiomer crystals, in which the R-helix of 1-D InSe anion is directed by the related clockwise (Δ) cations of [M(phen)(3)](2+) or the L-helix of 1-D anion is directed by the related anticlockwise (Λ) cation.

Indium sulfide clusters integrated with 2,2'-bipyridine complexes.

Supertetrahedral compounds of chalcogenometalates (T3 cluster compounds) integrated with Ni-bpy (bpy = 2,2'-bipyridine) complex were prepared by a solvothermal technique. The compound [Ni(bpy)(3)](3)[H(4)In(10)S(20)]·bpy·2EG·6H(2)O (Mb-InS-1) (EG = ethylene glycol) consists of discrete T3 clusters of [H(4)In(10)S(20)](6-) with three [Ni(bpy)(3)](2+) cations. The compound [Ni(bpy)(3)](2)[H(2)In(10)S(19)]·bpy·2HEA·2H(2)O (Mb-InS-2) (EA = ethanolamine) is a 1-D polymer, in which zigzag T3 cluster chains are charge balanced by metal-bpy complex cations.

Indium-sulfur supertetrahedral clusters integrated with a metal complex of 1,10-phenanthroline.

A new type of indium-sulfur supertetrahedral compound with unique optical absorption property has been synthesized and characterized crystallographically, in which discrete or polymeric InS-T3 clusters are integrated with metal complex cations of 1,10-phenanthroline.