Solvothermal syntheses and characterizations of three new holmium selenidostannates(iv): a rare example of adamantane-like [Sn₄Se₁₀]⁴⁻selenidostannate(iv) with lanthanide complexes

Abstract

Three new holmium selenidostannates(iv), [Ho(dap)4]2[Sn2Se6]Cl2 (, dap = diaminopropane), {[Ho(dien)2]2(μ2-OH)2}[Sn2Se6] (, dien = diethylenetriamine), and [Ho2(tepa)2(μ2-OH)2Cl2]2[Sn4Se10]·4H2O (, tepa = tetraethylenepentamine), have been solvothermally synthesized and structurally characterized. consists of two mononuclear [Ho(dap)4](3+) complex cations, one [Sn2Se6](4-) anion built up from two [SnSe4] tetrahedra sharing a common edge, and two Cl(-) ions. consists of one binuclear holmium(iii) complex {[Ho(dien)2]2(μ2-OH)2}(4+) cation and one dimeric [Sn2Se6](4-) anion. is composed of rare binuclear holmium(iii) complex [Ho2(tepa)2(μ2-OH)2Cl2](2+) cations, adamantane-like [Sn4Se10](4-) and free water molecules. Although a few chalcogenidostannates(iv) with lanthanide(iii) complex cations acting as counterions have been reported, their anions are strongly dominated by the dimeric [Sn2Se6](4-) moieties. represents a rare example of an adamantane-like [Sn4Se10](4-) selenidostannate with lanthanide complexes as counterions. The optical properties of have been investigated by UV-vis spectroscopy.

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

“…1d). The NÁÁÁCl distances are in the range of 3.228(5)-3.526(4) Å and the NÁÁÁSe distances vary from 3.589(4) to 3.701(4) Å , which are compared with those reported in the literature [19]. (Fig.…”

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“…[203] An oligoselenide containing the cluster [ n Pr4N]2[Ag4(Se4)3] (297, Figure 9) in analogy to the sulfide congener could also be obtained after using Na2Se5 as the selenide source. [204] The nitrogen bridged phophine selenide [Ag4{(SePPh2)2N}3](OTf) (298) is another example of a silver compound that can be prepared according to the synthesis used for its copper homolog. [205] Lastly, a second selenone [(AgPPh3)4(Mbis)3](OTf)4 (299, Mbis = 1,1´-methylenebis(3-methylimidazoline-2-selone)) unique to the chemistry with silver results from the addition of Mbis to [Ag(OTf)(PPh3)], which leads to an adamantane featuring PPh3 terminal ligands at the silver positions.…”

“…Te, [Ph4P]Br, thiophene, n BuLi / THF 2. AgNO3 / DMF C [203] Chemical Science Accepted Manuscript Please do not adjust margins Please do not adjust margins (298) Ag(OTf), K{(SePPh2)2N} / CH2Cl2, 30 min C [205] [(AgPPh3)4(Mbis)3](OTf)4 (299) [Ag(OTf)(PPh3)], Mbis / Me2CO, 1 h C [206] Me2phen = 2,9-dimethyl-1,10-phenanthroline, BIK = Bis(2-methyl-imidazol-2-yl)ketone,…”

“…[289,292,293] The family of clusters with metal complex counterions could also be expanded by starting from elements and binary precursors in solvothermal reactions (method B) to not only obtain more Ge clusters (552-556), [294][295][296][297] but also Sn congeners as well as rare earth containing examples(557-562). [298][299][300] In one case, the addition of antimony to such a reaction mix of GeO2 and elemental sulfur led to the formation of a compound with two distinct clusters, [(Me)2NH2]6[Ge2Sb2S7][Ge4S10] (563), one adamantane-type and another ternary molecule with noradamantane like topology. [301] Unlike the other compounds in this chapter, the oxo cluster compound [Mn(en)3]2[Ge4O6Te4] (564, Figure 12) deviates from the strict [Q4E10] 4− cluster buildup and carries terminal Te groups at the Q position.…”

“…GeO2, Sb, S, MCl2 / dap, 170 °C, 6 days B [295] [Ni2(µ-teta)(teta)2][Ge4S10] (555) GeO2, S, NiCl2, teta / H2O, 170 °C, 12 days B [296,297] [Ni(teta)2]2[Ge4Se10] (556) GeO2, Se, NiCl2, teta / H2O, 170 °C, 16 days B [296] [Ho2(tepa)2(OH)2Cl2]2[Sn4Se10] (557) SnCl4•H2O, Se, HoCl3 / tepa,170 °C, 6 days B [298] [Ni(teta)(en)][Ni(teta)(hda)][Sn4Se10] (558) Sn, Se, Ni(OAc)2, hda / teta, 170 °C, 5 days B [299] [Ln2(tepa)2(OH)2Cl2]2[Sn4Se10] (559-562, Ln = Y, Dy, Er, Tm) SnCl4•5H2O, Se, LnCl3, Ag / tepa, 180 °C, 6 days B [300]…”