Solvothermal Syntheses, Crystal Structures and Selected Optical Properties of [M(C₈N₅H₂₃)]₂Sn₂S₆ (M = Co, Fe, Ni; C₈N₅H₂₃ = tetraethylenepentamine)

Abstract

Three new thiostannates [Co(C8N5H23)]2Sn2S6 (I), [Fe(C8N5H23)]2Sn2S6 (II) and [Ni(C8N5H23)]2Sn2S6 (III) were synthesized under solvothermal conditions. In all compounds the [Sn2S6]4− anion acts as a bidentate or μ2 ligand bridging two symmetry related [M(C8N5H23)]2+ cations. Despite the identical building units only compounds I and II are isostructural crystallizing in the tetragonal space group I41/a, whereas compound III crystallizes in space group P21/n. A detailed analysis of the intermolecular interactions reveals remarkable differences between I/II and III which may be responsible for the crystallization in different symmetries and space groups. The slightly different bonding situations in the [Sn2S6]4− anion in I/II and III are reflected in the Raman spectra. For all three compounds the UV/Vis spectra show d‐d transitions energetically below the absorption edge.

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

“…S7). Angles around the Nd 3 þ ion are in the range of 65.45 (7)-118.16 (9) 103.48(6)-120.02 (7) Sn-S-Ln 89.04 (7) (Table 3) bond lengths are in consistent with corresponding values observed in the 8-fold coordinated Nd(III) complexes [12a,22]. The Nd-S [2.8946(13) Å] bond is slightly shorter than the Nd-S bond of the 9-fold coordinated Nd(III) complex of 1b ( The coordination polymers in 2a-2d are joined into 3-D networks via intermolecular hydrogen bonds.…”

“…In the case of tin chalcogenides, a number of binary chalcogenostannates had been prepared by the solvothermal methods using organic cations as templates [4]. When the mild solvothermal syntheses were conducted in the presence of transition metals (TMs) in coordinative aliphatic polyamines, a family of TM-contained chalcogenostannates were obtained [5][6][7][8][9][10]. The polyamines act as not only the reaction media, but also the chelating ligands to the TM centers to form [TM(polyamine) m ] n þ complex units during the solvothermal reaction.…”

“…But the syntheses in tridentate triethylenetetramine (trien) and tris(2-aminoethyl)amine (tren), and pentadentate tetraethylenepentamine (tepa) polyamines usually produced the chalcogenidostannates incorporated with TM-complex fragments via TM-Q bonds. The examples include {[Mn (trien)] 2 SnS 4 } Á 4H 2 O [7], [{TM(tren)} 2 (μ-Sn 2 S 6 )] (TM ¼Co, Ni) [8], [{TM(tepa)} 2 (μ-Sn 2 S 6 )] (TM¼ Fe, Co, Ni) [9], [{Zn(trien)} 2 (μ-SnTe 4 )], and [{Zn(tren)} 2 (μ-Sn 2 Te 6 )] [10]. The unsaturated coordination site of TM in the TM-amine fragments is completed by the chalcogen atom of the chalcogenidostannate anions.…”

Five dimeric thiogermanates with transition metal complexes of multidentate chelating amines: Syntheses, structures, magnetism and photoluminescence

“…The dual roles of [TM(L 4 )] n+ complexes in modifying the inorganic maingroup metal chalcogenide frameworks contribute to increased complexity and functionality of hybrid chalcogenides. In contrast, the L 5 -dentate chelating amine (tepa, for example) prefer to coordinate to TM ion to form [TM(L 5 )] n+ complex with only one free coordination site of the TM ion, which usually display structuredecorating groups in the chalcogenides, such as compounds 4a, 4b and several similar compounds in the literature [28,[70][71][72][73][74][75].…”

Solvothermal syntheses and characterizations of the first example of lanthanide selenidostannates prepared in mixed ethylene polyamines

“…But in the presence of tetradentate triethylenetetramine (trien) and tris(2-aminoethyl)amine (tren), and pentadentate tetraethylenepentamine (tepa) ligands, or bidentate ligands with higher steric hindrance (such as 1,10-Phenanthroline, phen), unsaturated TM-amine complexes can be formed, and TM-incorporated chalcogenidostannates are obtained. The examples include {[Mn(trien)] 2 SnS 4 }Á4H 2 O [11], [{TM(tren)} 2 (l-Sn 2 S 6 )] (TM = Co, Ni) [12], [{TM(tepa)} 2 (l-Sn 2 S 6 )] (TM = Fe, Co, Ni) [13], [{TM(phen)} 2 (l-Sn 2 Se 6 )] (TM = Mn, Fe) [14], [{Zn(trien)} 2 (l-SnTe 4 )], and [{Zn(tren)} 2 (l-Sn 2 Te 6 )] [15]. The unsaturated coordination site of TM center in TM-amine complexes is completed by the chalcogen atom of the chalcogenidostannate anions in these compounds.…”