Heterometallic Clusters [CuSn₃S₉]⁵⁻ and [Cu₆Sn₆S₂₀]¹⁰⁻: Solvothermal Synthesis and Characterization of 4f–3d Thiostannates

Abstract

Two types of 4f-3d thiostannates with general formula [Hen]₂[Ln(en)₄(CuSn₃S₉)]∙0.5 en (Ln1; Ln=La, 1; Ce, 2) and [Hen]₄[Ln(en)₄]₂[Cu₆Sn₆S₂₀]∙3 en (Ln2; Ln=Nd, 3; Gd, 4; Er, 5) were prepared by reactions of Ln₂O₃, Cu, Sn, and S in ethylenediamine (en) under solvothermal conditions between 160 and 190 °C. However, reactions performed in the range from 120 to 140 °C resulted in crystallization of [Sn₂S₆]⁴⁻) compounds and CuS powder. In 1 and 2, three SnS₄ tetrahedra and one CuS₃ triangle are joined by sharing sulfur atoms to form a novel [CuSn₃S₉]⁵⁻ cluster that coordinates to the Ln(3+) ion of [Ln(en)₄]³⁺ (Ln=La, Ce) as a monodentate ligand. The [CuSn₃S₉]⁵⁻ unit is the first thio-based heterometallic adamantane-like cluster coordinating to a lanthanide center. In 3-5, six SnS₄ tetrahedra and six CuS₃ triangles are connected by sharing common sulfur atoms to form the ternary [Cu₆Sn₆S₂₀ ]¹⁰⁻ cluster, in which a Cu₆ core is enclosed by two Sn₃S₁₀ fragments. The topological structure of the novel Cu₆ core can be regarded as two Cu₄ tetrahedra joined by a common edge. The Ln³⁺ ions in Ln1 and Ln2 are in nine- and eightfold coordination, respectively, which leads to the formation of the [CuSn₃S9]⁵⁻ and [Cu₆Sn₆S₂₀]¹⁰⁻ clusters under identical synthetic conditions. The syntheses of Ln1 and Ln2 show the influence of the lanthanide contraction on the quaternary Ln/Cu/Sn/S system in ethylenediamine. Compounds 1-5 exhibit bandgaps in the range of 2.09-2.48 eV depending on the two different types of clusters in the compounds. Compounds 1, 3, and 4 lost their organic components in the temperature range of 110-350 °C by multistep processes.

Complexations of Ln(III) with SnS4H and Sn2S6: Solvothermal syntheses and characterizations of lanthanide coordination polymers with thiostannate and polyamine mixed ligands

“…S5 in the SI). The La-N [2.697 (7) À 2.775(8) Å], and La-S [3.014(2), 3.052(2) Å] ( Table 2) bond lengths are comparable to the corresponding bond lengths observed in the mixed La(III) complex [Hen] 2 [La(en) 4 (CuSn 3 S 9 )] Á 0.5en, respectively [20].…”

Ternary Mixed‐Valence Organotin Copper Selenide Clusters

“…The family of discrete metal chalcogenide clusters with aternary inorganic core comprises ad iversity of structural motifs and compositions, ranging from ligand-stabilized neutral heterocubanes [1][2][3][4] to huge anionic supertetrahedra, [5][6][7] and from clusters of moderate size [8] to compounds on an anometer scale. [9,10] These feature combinations of different transition metal atoms [11][12][13][14] or different main group metal atoms, [15] or both, [16][17][18][19] or they combinea toms of transition metals and lanthanides.…”

Solvothermal Syntheses and Characterization of a Series of New Selenidostannates with Lanthanide Complexes as Counterions

“…The lamp was kept on continuously, and a manual shutter was used to block exposure of the sample to the light. The sample was typically irradiated at intervals of 60 s. (6) 10.2401 (14) 10.2141 (13) 10.2038 (17) b (Å ) 14.1276 (9) 14.1163 (19) 14.1184 (18) 14.176 (3) c (Å ) 18.0682 (11) 18.030 (3) 18.000 (2) 18.041 (3) b (°)…”

“…Unsaturated TMCs that act as either decorating groups or bridging groups can bond directly to [Sn 2 Q 6 ] 4-anions to form a new class of organic hybrid chalcogenidostannates, as exemplified by [{Mn(en) 2 } 2 (l-en) (l-Sn 2 S 6 )] [11], [{M(tren)} 2 (l-Sn 2 S 6 )] (tren = tris(2-aminoethyl)amine; M = Ni and Co) [2a], and [M(tepa)] 2 (l-Sn 2 Se 6 ) (tepa = tetraethylenepentamine; M = Fe, Co, Mn) [12,13]. Compared with the overwhelming chalcogenido-stannates containing TMCs, lanthanoid chalcogenidostannates are less explored under mild solvothermal conditions [14][15][16], mainly because they are comparatively unstable with respect to heat, water, oxygen, and light [17]. More recently, we have attempted the preparation of lanthanoid chalcogenidostannates in chelating amine solutions by the solvothermal methods, and prepared a series of lanthanoid chalcogenidostannates containing [Sn 2 Q 6 ] 4-anions [Y 2 (dien) 4 (l-OH) 2 ]Sn 2 S 6 [18], (tetaH) 2 [Ln 2 (teta) 2 (tren) 2 (l-Sn 2 S 6 )]Sn 2 S 6 (Ln = Eu, Sm) [18], [Eu 2 (tepa) 2 (l-OH) 2 (l-Sn 2 S 6 )]-(tepa) 0.…”