Litao An

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), [Y(2)(dien)(4)(μ-OH)(2)]Sn(2)S(6) (1, dien = diethyl-enetriamine), (tetaH)(2)[Ln(2)(teta)(2)(tren)(2)(μ-Sn(2)S(6))]Sn(2)S(6) [Ln = Eu (2), Sm (3); teta = triethylenetetramine; tren = tris(2-aminoethyl)amine] and [Eu(2)(tepa)(2)(μ-OH)(2)(μ-Sn(2)S(6))](tepa)(0.5)·H(2)O (4, tepa = tetraethylene-pentamine) were solvothermally synthesized and structurally characterized. 1 consists of a binuclear [Y(2)(dien)(4)(μ(2)-OH)(2)](4+) cation and a discrete dimeric [Sn(2)S(6)](4-) anion. Both 2 and 3 are isostructural and composed of [Ln(2)(teta)(2)(tren)(2)(μ-Sn(2)S(6))](2+) cations, protonated triethylenetetramines (tetaH), and discrete dimeric [Sn(2)S(6)](4-) anions. A Sn(2)S(6)(4-) anion bridges two [Ln(teta)(tren)](3+) cations via the trans-S(t) (t = terminal) atoms to form the first examples of inorganic-organic hybrid thiostannate cations [Ln(2)(teta)(2)(tren)(2)(μ-Sn(2)S(6))](2+). 4 consists of one-dimensional (1-D) neutral chains [Eu(2)(tepa)(2)(μ-OH)(2)(μ-Sn(2)S(6))](n) built up from the linkage of dinuclear complex cations [Eu(2)(tepa)(2)(μ(2)-OH)(2)](4+) and bridging anions [Sn(2)S(6)](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.

Solvothermal synthesis and characterization of two 2-D layered germanium thioantimonates with transition-metal complexes

Two germanium thioantimonates [Co(dien)(2)](2)GeSb(4)S(10) (1, dien = diethylenetriamine) and [Mn(en)(3)]GeSb(2)S(6) (2, en = ethylenediamine) have been solvothermally synthesized and characterized by IR, UV/Vis, fluorescence spectroscopy, elemental analysis, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. 1 contains heterometallic pseudosemicube [GeSb(2)S(7)] clusters and chain-like Sb(4)S(10) tetramers, which are interconnected to form a unique double layer of [GeSb(4)S(10)](4-) with 10-MR helical channels. 2 features a sheet layer of [GeSb(2)S(6)](2-) with ellipse-like 12-MR, where one [GeS(4)] tetrahedra, one [SbS(3)] trigonal-pyramid and one Ψ-[SbS(4)] trigonal bipyramid are combined to form another heterometallic [GeSb(2)S(8)] cluster as a building unit. 1 and 2 exhibit absorption edges at 2.36 eV and 2.10 eV, respectively. 2 exhibits a fluorescence emission at room temperature.

Solvothermal synthesis, crystal structures and properties of three new thiogermanates: the only example of the thiogermanate anion [Ge2S6]4− as a bridging ligand to a lanthanide complex ion

Three new thiogermanates, (trenH2)2[Ge2S6] (1, tren = tris(2-aminoethyl)amine), [Eu(dien)3]2[Ge2S6]Cl2 (2, dien = diethylenetriamine) and [Y2(tepa)2(μ-OH)2(μ-Ge2S6)](tepa)0.5·H2O (3, tepa = tetraethylenepent-amine), were solvothermally synthesized and characterized. Both 1 and 2 are composed of discrete [Ge2S6]4− anions, while 3 contains a bridging [Ge2S6]4− anion as a μ2-ligand with trans terminal S atoms linking [Y2(OH)2(tepa)2]4+ groups, which is the only example of germanium chalcogenide anions acting as bridging ligands to a lanthanide complex ion. The optical absorption spectra indicate that they are wide band-gap semiconductors and their thermal stabilities have been investigated by thermogravimetric analyses (TGA).

The syntheses, structures and properties of three new lanthanoid thioarsenates: the only example of thioarsenate acting as a ligand to a lanthanide complex

Three new lanthanoid thioarsenates [Eu(en)3(η²-AsS₄)] (1, en = ethylenediamine), [Er(teta)(en)(η²-AsS₄)] (2, teta = triethylenetetramine) and [La₂(tepa)₂(μ-η¹,η³-AsS₃)₂] (3, tepa = tetraethylenepentamine) have been solvothermally synthesized and structurally characterized. In compounds 1 and 2, the tetrathioarsenate [AsS₄]³⁻ anions act as η²-AsS₄ chelating ligands to the lanthanide complexes [Eu(en)₃]³⁺/[Er(teta)(en)]³⁺, leading to neutral molecules [Eu(en)₃(η²-AsS₄)]/[Er(teta)(en)(η²-AsS₄)], whereas the [AsS₃]³⁻ anion in compound 3 acts as a μ-η¹,η³-AsS₃ tetradentate bridging ligand to link [La(tepa)]³⁺ ions into neutral centrosymmetric [La₂(tepa)₂(μ-η¹,η³-AsS₃)₂] moieties, where a new coordination mode of μ-η¹,η³-AsS₃ is observed for the [AsS₃]³⁻ ligand. Compounds 1-3 are the only examples of solvothermally synthesized thioarsenates where the [AsS₄]³⁻/[AsS₃]³⁻ anions act as ligands in the lanthanide complex. Compound 1 exhibits a fluorescence emission at room temperature. Density functional theory calculations for compounds 2 and 3 also have been performed, and the absorption edges of compounds 1-3 have been investigated by UV-vis spectroscopy.

A series of new lanthanoid thioantimonates: a rare example of organic-decorated cationic lanthanoid thioantimonate chains based on asymmetric dinuclear lanthanide complexes

A series of new lanthanoid thioantimonates [Ln(teta)2]SbS4 [teta = triethylenetetramine; Ln = Eu (1), Gd (2), Er (3)], {[Ln(tepa)]2[μ2-SbIIIS3](μ2-OH)}2{[Ln(tepa)]2(μ2-OH)2(SbVS4)2}Cl2 [tepa = tetraethylene-pentamine; Ln = Y(4), Eu(5), Er(6)], and [Gd2(tepa)2(μ2-OH)2(μ2-SbS4)]Cl·0.25H2O (7) were synthesized via reactions of Sb, S and LnCl3 in teta or tepa under solvothermal conditions and were structurally characterized. Compounds 1–3 consist of isolated [Ln(teta)4]3+ cations and tetrahedral [SbS4]3− anions. Compounds 4–6 contain heterometallic mixed amino-thiocluster cations {[Ln(tepa)]2[μ2-SbS3](μ2-OH)}2+, heterometallic anions {[Ln2(tepa)2(μ2-OH)2](SbS4)2}2− and free Cl− ions, which provide a rare example of the coexistence of noncondensed pyramidal [SbIIIS3]3− and tetrahedral [SbVS4]3− anions in a single thioantimonate. 7 consists of a 1-D polymeric cation [Gd2(tepa)2(μ2-OH)2(μ2-SbS4)]+, constructed through the linkage of asymmetric dinuclear gadolinium complex [Gd2(tepa)2(μ2-OH)2]4+ cations, tetrahedral [SbVS4]3− anions and a Cl− ion and water molecule, which represents a rare example of organic-decorated cationic lanthanoid thioantimonate chains based on asymmetric dinuclear lanthanide complexes. The present compounds exhibit semiconducting properties with absorption band edges between 2.00 and 3.03 eV.

A series of new 3-D boratopolyoxovanadates containing five types of [KxOy]n building units

A series of new 3-D boratopolyoxovanadates {K2V12B18O54(OH)6(H2O)[K8(H2O)16]}·3H2O (1), {K10V12B18O54(OH)6(H2O)}·14H2O (2), {V12B18O54(OH)6(H2O)[K6(H2O)12]}·2(H2dien)·3H2O (3, dien = diethylenetriamine), {V6B20O44(OH)8(H2O)[K8(H2O)6]} (4), and {V6B20O44(OH)8(H2O)[K(H2O)]2}·2(H3dien)·6H2O (5) have been hydrothermally synthesized and structurally characterized. These compounds contain five types of [KxOy]n building units, namely, a dimeric [K2O16] unit for 5, a 1-D [K3O12]n chain for 3, a 3-D [K5O10]n sub-network for 1, a 3-D [K5O12]n sub-network for 2, and a 3-D [K4O7]n sub-network for 4. The 3-D frameworks of both 1 and 2 are built up from a different 3-D inorganic [KxOy]n sub-network and entrapped [V12B18O54(OH)6(H2O)]10− (denoted as [V12B18]) clusters, respectively. 3 contains [V12B18] clusters and 1-D [K3O12]n chains, which are interconnected to form a 3-D {V12B18O54(OH)6(H2O)[K6(H2O)12]}n architecture with 1-D tunnels filled with protonated H2dien2+ ions. The 3-D architecture of 4 is constructed by another rare 3-D inorganic [K4O7]n sub-network and entrapped [V6B20O44(OH)8(H2O)] (denoted as V6B20) clusters. Compounds 1, 2 and 4 represent rare examples of extended POVs with the 3-D inorganic [KxOy]n sub-networks. 5 contains [V6B20] clusters and dimeric [K2O16] units, which are interconnected to give a 3-D {B20V6O44(OH)8(H2O)[K(H2O)]2}n architecture with 1-D tunnels filled with protonated H3dien3+ ions. Although a few boratopolyoxovanadates contain the [V6B20] cluster, they display either a discrete [V6B20] cluster or a low-dimensional extended structure. Therefore, both 4 and 5 are rare examples of 3-D boratopolyoxovanadate architectures based on the [V6B20] clusters. The magnetic susceptibilities of both 4 and 5 show the antiferromagnetic interaction between VIV cations. Their spectroscopic properties were also investigated.

A New 1D Polyoxovanadate (Cu(en)2V10O28)(Cu(en)2(H2O))2 2H3BO3 2H2O Containing the Rarely Non-condensed Boric acid

A new 1D polyoxovanadate containing boric acid [Cu(en)2V10O28][Cu(en)2(H2O)]2 2H3BO3 2H2O (1, en=ethylenediamine) has been hydrothermally synthesized and structurally characterized. Compound 1 consists of a polyoxovanadate chain [Cu(en)2V10O4-28 ]n based on the linkage of decavanadate clusters and [Cu(en)2]2+ groups, complex cations [Cu(en)2(H2O)]2+, free H3BO3 and H2O molecules. The polyoxovanadates and boric acid can undergo polycondensation into various B-O-V clusters under hydrothermal conditions, but 1 is the only example of the non-condensation of polyoxovanadate and boric acid. The IR spectrum and the thermal behavior of 1 were also studied Graphical Abstract A New 1D Polyoxovanadate [Cu(en)2V10O28][Cu(en)2(H2O)]2 2H3BO3 2H2O Containing the Rarely Non-condensed Boric acid

CCDC 848793: Experimental Crystal Structure Determination

Related Article: Jian Zhou, Xing Liu, Litao An, Feilong Hu, Wenbin Yan, Yunyan Zhang|2012|Inorg.Chem.|51|2283|doi:10.1021/ic2023083