Synthesis and characterization of inorganic-organic hybrid gallium selenides

Two semiconducting hybrid gallium selenides, [Ga6Se9(C6H14N2)4][H2O] (1) and [C6H14N2][Ga4Se6(C6H14N2)2] (2), were prepared using a solvothermal method in the pres-ence of 1,2-diaminocyclohexane (1,2-DACH). Both materials consist of neutral inorganic layers, in which 1,2-DACH is co-valently bonded to gallium. In (1), the organic amine acts as a monodentate and a bidentate ligand, while in (2) bidentate and uncoordinated 1,2-DACH molecules coexist.

Structural complexity in indium selenides prepared using bicyclic amines as structure-directing agents

The synthesis and characterization of five new indium selenides, [C9H17N2]3[In5Se8+x(Se2)1−x] (1–2), [C6H12N2]4[C6H14N2]3[In10Se15(Se2)3] (3), [C6H14N2][(C6H12N2)2NaIn5Se9] (4) and [enH2][NH4][In7Se12] (5), are described. These materials were prepared under solvothermal conditions, using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,4-diazabicyclo[2.2.2]octane (DABCO) as structure-directing agents. Compounds 1–4 represent the first examples of ribbons in indium selenides, and 4 is the first example of incorporation of an alkali metal complex. Compounds 1, 2 and 4 contain closely related [In5Se8+x(Se2)1−x]3− ribbons which differ only in their content of (Se2)2− anions. These ribbons are interspaced by organic countercations in 1 and 2, while in 4 they are linked by highly unusual [Na(DABCO)2]+ units into a three-dimensional framework. Compound 3 contains complex ribbons, with a long repeating sequence of ca. 36 Å, and 4 is a non-centrosymmetric three-dimensional framework, formed as a consequence of the decomposition of DABCO into ethylenediamine (en) and ammonia.

Polymorphism and optical properties in [NH4][InSe2]

The solvothermal synthesis and characterization of two indium selenides with stoichiometry [NH4][InSe2] is described. Yellow [NH4][InSe2] (1), which exhibits a layered structure, was initially prepared in an aqueous solution of trans-1,4-diaminocyclohexane, and subsequently using a concentrated ammonia solution. A red polymorph of one-dimensional character, [NH4][InSe2] (2), was obtained using 3,5-dimethylpyridine as solvent. [NH4][InSe2] (1) crystallizes in the non-centrosymmetric space group Cc (a=11.5147(6), b=11.3242(6), c=15.9969(9) Å and β=100.354(3)°). The structural motif of the layers is the In4Se10 adamantane unit, composed of four corner-linked InSe4 tetrahedra. These units are linked by their corners, forming [InSe2]− layers which are stacked back to back along the c-direction, and interspaced by [NH4]+cations. The one-dimensional polymorph, (2), crystallizes in the tetragonal space group, I4/mcm (a=8.2519(16), c=6.9059 (14) Å). This structure contains infinite chains of edge-sharing InSe4 tetrahedra separated by [NH4]+ cations.