Feilong Hu

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.

Second ligands-assisted structural variation of entangled coordination polymers with polycatenated or polythreaded features

The self-assembly of transition metal salts with dicarboxylate ligands and second ligands afford a series of entangled coordination frameworks based on different metal clusters, namely, [Ni2(oba)2(bpy)2(H2O)2]·(DMF)(H2O)2 (1), [Ni2(oba)2(bpy)2(sa)(H2O)2]·(H2O)4 (2), [Cu5(oba)4(bpy)5(pca)2(H2O)4]·(H2O)9 (3), [Co3(oba)2(bpy)2(dbca)2]·(H2O)6 (4), [Co3(oba)2(dbca)2(H2O)] (5) and [Co3(oba)2(bph)2(SO4)]·(H2O)4 (6) [oba = 4,4′-oxydibenzoic acid; bpy = 4,4′-bipyridine; dbca = [1,1′-biphenyl]-2,2′-dicarboxylic acid; sa = 2-hydroxybenzoic acid; pca = picolinic acid; bph = (1E,2E)-1,2-bis(pyridin-4-ylmethylene)hydrazine]. Their structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR spectra and TG analyses. The auxiliary ligands play important roles in the formation of various entangled networks. 1 shows a box-like structure and is interlocked in a parallel fashion. Compound 2 represents the first example of a 3D polycatenated framework with different size arms. 3 displays 2D → 3D entangled polymers with polycatenated and polythreaded features based on 4,4-sql layers, which are formed by short/long alternate pillars. 4 shows an interesting framework of 2D → 3D polythreading feature with a Co3 cluster occupying the corner of the grid. However, 5 displays 3D polycatenation with a 1D zigzag metal chain. An unusual [Co3SO4] unit, which is linked by four bph ligands and four oba ligands, exhibiting an anionic three-dimensional (3D) framework is observed in 6. Compounds 4–6 display antiferromagnetic properties.

One novel 3-D vanadoborate with unusual 3-D Na–O–Na network

A new 3-D vanadoborate {Na2B18V12O54(OH)6(H2O)[Na8(H2O)16]}·2H2O (1) has been hydrothermally synthesized and structurally characterized. The crystal of 1 is built up from an unusual 3-D Na–O–Na network and entrapped [V12B18O54(OH)6(H2O)]10− clusters (denoted [V12B18]). Such a Na–O–Na network is constructed by the linkage of rare 1-D helical [Na4(H2O)84+]n chains and [NaO6] octahedra. 1 represents the rare example of extended POMs with 3-D inorganic metal–oxygen networks. Magnetic measurements illustrate that 1 has antiferromagnetic exchange interactions between metal centers.

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.

New 3-D polyoxovanadoborate architectures based on [V12B18O60]16− clusters

Three new 3-D polyoxovanadoborates {[Cu(dien)(H2O)]3V12B18O54(OH)6(H2O)}·4H3O·5.5H2O (1, dien = diethylenetriamine), {[Cd(H2O)2]3V12B18O54(OH)6(H2O)}·4H3O·9.5H2O (2) and {[Na(H2O)3]4Na2V12B18O56(OH)4(H2O)}(H3dien)2 (3) have been hydrothermally synthesized and structurally characterized. Compounds 1–3 contain vanadoborate cluster [V12B18O60] constructed by two hexameric oxovanadate units [V6O9] and one puckered [B18O42] ring via sharing O atoms. The vanadoborate cage [V12B18O60] can present different degrees of protonation, namely [V12B18O60H6]10− for 1 and 2, [V12B18O60H4]12− for 3. The clusters [V12B18O60H6]10− in 1 are connected by complex cations [Cu(dien)(H2O)]2+ into a new 3-D framework via all terminal O atoms of square-pyramidal [VO5] groups, while the clusters [V12B18O60H6]10−/[V12B18O60H4]12− in 2 and 3 are linked with [Cd(H2O)2]2+ groups/the combination of [Na(H2O)3]+ and Na+ ions to give another two types of new 3-D frameworks via O atoms of [BOx] (x = 3, 4) polyhedra, respectively. Magnetic measurements illustrate that compounds 1 and 2 have antiferromagnetic exchange interactions between metal centers. The theoretical band structure of 2 has been also studied.

A novel 3-D chiral polyoxovanadate architecture based on breaking high symmetry of spherical [V15O36Cl]8− cluster

A novel 3-D chiral polyoxovanadate {[Zn(en)2]2V15O36Cl}[Zn(en)2(H2O)]2·3H2O (1, en = ethylenediamine) has been hydrothermally synthesized under spontaneous resolution without any chiral source. The unique 3-D chiral architecture of 1 is built up from destroying high symmetry of the spherical [V15O36Cl]8− cluster. Magnetic measurements illustrate that 1 has antiferromagnetic exchange interactions between metal centers.

Solvothermal Syntheses and Characterization of Three Lanthanide Thioantimonates(V) with Mixed Ethylene Polyamines

Three new lanthanide thioantimonates(V) [Ln(en)(teta)(SbS4)] {Ln=Sm (1), Eu (2), Gd (3); en=ethylenediamine; teta=triethylenetetramine} have been solvothermally synthesized and structurally characterized. Compounds 1 - 3 are isostructural. The [SbS4]3- anion acting as bichelating ligand is bound to the [Ln(en)(teta)]3+ ion, resulting in a neutral complex [Ln(en)(teta)(SbS4)]. The central Ln3+ ion lies within an eight-coordinate environment forming a distorted bicapped trigonal prism LnN6S2. Although a few lanthanide thioantimonates have been reported to date, they only contain one type of ethylene polyamine. Compounds 1 - 3 are rare examples of lanthanide thioantimonates with mixed ethylene polyamine ligands. The absorption edges of 1:75 eV for 1 and 2:27 eV for 3 have been derived from optical absorption spectra. Graphical Abstract Solvothermal Syntheses and Characterization of Three Lanthanide Thioantimonates(V) with Mixed Ethylene Polyamines

A novel 1-D telluridoindate based on rare tetramer [In4Te10]4− unit with photocatalytic properties

A novel 1-D telluridoindate [In3Te5(dien)]·H3O·H2O (1, dien = diethylenetriamine) has been solvothermally prepared and structurally characterized. 1 features infinite railway-like chains constructed by the linkage of unprecedented tetramer [In4Te10]4− units and [In(dien)]3+ groups. The absorption band edge of 1 is 2.16 eV, exhibiting properties of the semiconductor. Photocatalytic experiments have shown the ability of 1 in photodegradation of Methyl orange (MO) and Rhodamine B (RhB), which selectively degradation of MO.