Solvothermal Synthesis and Characterization of Lanthanide Chalcogenidostannates [Ln₂(en)₆(μ₂‐OH)₂][Sn₂S₆] (Ln = Dy, Er) and [Dy₂(en)₆(μ₂‐OH)₂][Sn₂Se₆]

Abstract

New lanthanide chalcogenidostannates [Ln 2 (en) 6 (µ 2 -OH) 2 ]-[Sn 2 S 6 ] (Ln ϭ Dy (1), Er (2)) and [Dy 2 (en) 6 (µ 2 -OH) 2 ][Sn 2 Se 6 ] (3) (en ϭ ethylenediamine) were synthesized by reactions of SnCl 4 and S (or Se) with Ln 2 O 3 oxides under the mild solvothermal conditions. Compounds 1-3 are isostructural and consist of a binuclear lanthanide(III) complex cation [Ln 2 (en) 6 (µ 2 -OH) 2 ] 4ϩ and a dimeric anion [Sn 2 E 6 ] 4Ϫ (E ϭ S, Se). The anion is composed of two SnE 4 tetrahedra sharing a common edge with C 2h symmetry. All the lanthanide(III) atoms are eight-coordinate by six nitrogen atoms of * Ding-Xian Jia College

Effect of lanthanide contraction on the Ln/Sb/Se/dien system: solvothermal syntheses and characterizations of lanthanide(III)-selenidoantimonate complexes with diethylenetriamine as a co-ligand

“…The soft Lewis base SbSe 4 3À binds with Ln(III) of the Ln-dien complexes to complete coordination around Ln(III), forming [Ln(dien) 2 (μ-η 1 ,η 2 -SbSe 4 )] n (1, 2) and [Ln(dien) 2 (η 2 -SbSe 4 )] (3,4). Our present and previous work have shown that the Ln 2 O 3 /polyamine (polyamine = en, dien, and trien) system is convenient sources of lanthanide(III)-polyamine complexes under solvothermal conditions [17][18][19][20][21][22][23][24][25][26][27]. Heated under a N 2 atmosphere, 1-4 lose their dien components in one step at 215-256°C.…”

“…Recently, we have demonstrated that the solvothermal synthesis is a successful approach to ternary lanthanide chalcogenidometalates by using lanthanides instead of TMs in the solvothermal reactions, and have synthesized lanthanide(III)-containing chalcogenidogermanates [17], chalcogenidostannates [18][19][20][21], chalcogenidoarsenates [22,23], and chalcogenidoantimonates [24][25][26][27] in en or dien solvents. In the case of chalcogenidoantimonates, the Ln/Sb/Se system has been systematically investigated in en solvent across the lanthanide series and two structural types of lanthanide selenidoantimonates, Ln(en) 4 (SbSe 4 )] (Ln = La-Nd) and [Ln(en) 4 ]SbSe 4 ·0.5en (Ln = Sm-Yb), were obtained [24,25].…”

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

“…Unfortunately, solvothermal syntheses applying transition metals and structure-directing amines very often yield separated T M n+ complexes without any bonding to the anionic network, and discrete thiostannate anions. We note that thiostannate chemistry was extended very recently by the application of lanthanoid complexes Ln 3+ as charge-compensating cations [103,104]. In these compounds the Ln 3+ -centered complexes have no bonds to the thiostannate anions like in many T M n+ containing compounds.…”

The First Tetradentate μ‐1κ2:2κ2‐Sn2Se6 Ligand to a Lanthanide(III) Center: Solvothermal Syntheses and Characterizations of Lanthanide Selenidostannate Polymers with Tetraethylenepentamine as a Second Ligand

“…That is, the chain is based on repeating [La(tepa)‐Sn 2 Se 6 ] units (Figure 2). The [Sn 2 Se 6 ] 4– unit exhibits Sn–Se bond lengths in the range of 2.4596(17)–2.5919(17) Å and Se–Sn–Se angles in the range of 93.69(5)–116.37(6)° (Table 1), which indicates that the SnSe 4 tetrahedron in μ‐1κ 2 :2κ 2 ‐Sn 2 Se 6 is more distorted than that in free [Sn 2 Se 6 ] 4– anions 16,17. The La 3+ ion is in a nine‐coordinate environment involving five N atoms from a tepa ligand and four Se atoms from two Sn 2 Se 6 units.…”

“…In the course of our investigations of the complexation of chalcogenidometalate anions with Ln 3+ centers, we recently prepared Ln chalcogenidostannates [{Ln(dien) 2 } 4 (μ 4 ‐Sn 2 Se 9 )(μ‐Sn 2 Se 6 )] n (Ln = La, Ce, Nd) and [H 2 dien] 0.5 [Ln(dien) 2 (μ‐SnSe 4 )] (Ln = Sm, Eu, Gd) using dien as a solvent,15 in which the novel μ 4 ‐Sn 2 Se 9 , μ‐Sn 2 Se 6 , and μ‐SnSe 4 bridging or chelating ligands are observed. Comparably, Ln–en complexes lead to the formation of ionic compounds [{Ln(en) 4 } 2 (μ‐Se 2 )][Sn 2 Se 6 ] (Ln = La, Ce), [Ln 2 (en) 6 (μ 2 ‐OH) 2 ][Sn 2 Se 6 ] (Ln = Nd, Gd, Dy), and [Ln 2 (en) 6 (μ 2 ‐OH) 2 ][Sn 2 S 6 ] (Ln = Dy, Er), which contain discrete [Sn 2 S 6 ] 4– and [Sn 2 Se 6 ] 4– anions 15,16. It can be seen that the denticities of ethylenepolyamines significantly influence the solvothermal synthesis of Ln chalcogenidostannates.…”