Inorganic Chemistry, Vol.51, No.4, 2283-2290, 2012
Solvothermal Synthesis and Characterization of a Series of Lanthanide Thiostannates(IV): The First Examples of Inorganic-Organic Hybrid Cationic Lanthanide Thiostannates(IV)
A series of new lanthanide thiostannates(IV), [Y-2(dien)(4)(mu-OH)(2)]Sn2S6 (1, dien = diethyl-enetriamine), (tetaH)(2)[Ln(2)(teta)(2)(tren)(2)(mu-Sn2S6)]Sn2S6 [Ln = Eu (2), Sm (3); teta = triethylenetetramine; tren = tris(2-aminoethyl)amine] and [Eu-2(tepa)(2)(mu-OH)(2)(mu-Sn2S6)]-(tepa)(0.5)center dot H2O (4, tepa = tetraethylene-pentamine) were solvothermally synthesized and structurally characterized. I consists of a binuclear [Y-2(dien)(4)(mu(2)-OH)(2)](4+) cation and a discrete dimeric [Sn2S6](4-) anion. Both 2 and 3 are isostructural and composed of [Ln(2)(teta)(2)(tren)(2)(mu-Sn2S6)](2+) cations, protonated triethylenetetramines (tetaH), and discrete dimeric [Sn2S6](4-) anions. A Sn2S64- anion bridges two [Ln(teta)(tren)](3+) cations via the trans-S-t (t = terminal) atoms to form the first examples of inorganic organic hybrid thiostannate cations [Ln(2)(teta)(2)(tren)(2)(mu-Sn2S6)](2+). 4 consists of one-dimensional (1-D) neutral chains [Eu-2(tepa)(2)(mu-OH)(2)(mu-Sn2S6)](n) built up from the linkage of dinuclear complex cations [Eu-2(tepa)(2)(mu(2)-OH)(2)](4+) and bridging anions [Sn2S6](4-), free tepa molecules, and lattice water molecules. The present compounds exhibit wide-band gap semiconducting properties with absorption band edges between 2.40 and 2.91 eV.