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), [Y2(dien)4(μ-OH)2]­Sn2S6 (1, dien = diethyl-enetriamine), (tetaH)2[Ln2(teta)2(tren)2(μ-Sn2S6)]­Sn2S6 [Ln = Eu (2), Sm (3); teta = triethylenetetramine;
tren = tris­(2-aminoethyl)­amine] and [Eu2(tepa)2(μ-OH)2(μ-Sn2S6)]­(tepa)0.5·H2O (4, tepa = tetraethylene-pentamine)
were solvothermally synthesized and structurally characterized. 1 consists of a binuclear [Y2(dien)4(μ2-OH)2]4+ cation and a discrete
dimeric [Sn2S6]4– anion. Both 2 and 3 are isostructural and composed of [Ln2(teta)2(tren)2(μ-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-St (t = terminal) atoms to form the first examples of inorganic–organic
hybrid thiostannate cations [Ln2(teta)2(tren)2(μ-Sn2S6)]2+. 4 consists of one-dimensional (1-D) neutral
chains [Eu2(tepa)2(μ-OH)2(μ-Sn2S6)]n built up from
the linkage of dinuclear complex cations [Eu2(tepa)2(μ2-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.