Rongqing Zhao

A series of new lanthanoid thioarsenates: insights into the influence of lanthanide contraction on the formation of new lanthanoid thioarsenates.

A series of new lanthanoid thioarsenates [Ln(teta)(μ-η(1):η(2):η(1)-As(III)S3)]n {Ln = Ce (Ia), Pr (Ib), Nd (Ic), and Sm (Id); teta = triethylenetetramine} and [Ln(teta)(en)(μ-η(1):η(1):η(1)-As(V)S4)]n {Ln = La (IIa), Ce (IIb), Pr (IIc), and Nd (IId); en = ethylenediamine} were prepared by the solvothermal reaction of K3AsO3, S, LnCl3 and organic amines and structurally characterized. Compounds Ia–d crystallise in the orthorhombic space group Aba2 and display 1-D neutral chains [Ln(teta)(μ-η(1):η(2):η(1)-As(III)S3)]n, which represent the first examples of 1-D organic hybrid lanthanoid sulfides built up from trigonal-pyramidal [As(III)S3](3-) acting as tetradentate bridging ligands to interlink [Ln(teta)](3+) ions, while compounds IIa–d crystallise in the orthorhombic space group P2(1)2(1)2(1) and consist of other 1-D neutral chains [Ln(teta)(en)(μ-η(1):η(1):η(1)-As(V)S4)]n, which are built up from the linkages of the tetrahedral [As(V)S4](3-) ion and the [Ln(teta)(en)](3+) ion. To learn more about the influence of lanthanide contraction on the formation of lanthanoid thioarsenates, three organic hybrid lanthanoid thioarsenates [Ln(teta)(en)As(V)S4] [Ln = Dy (IIIa), Ho (IIIb), and Tm (IIIc)] with the neutral molecular structure type in the monoclinic centrosymmetric space group P2(1)/c are also presented. Their optical and magnetic properties have been investigated, and density functional theory calculations of Ia and IIa have also been performed.

Solvothermal syntheses of lanthanide thiogermanates displaying three new structural moieties

A series of lanthanide thiogermanates [Ln(dien)3]2[Ge2S6]Cl2 [Ln = Pr (Ia), Sm (Ib), Gd (Ic), Dy (Id); dien = diethylenetriamine], [Er2(dien)4(μ-OH)2][Ge2S6] (II) and [Ho(trien)(en)GeS3(SH)] (III, trien = triethylenetetramine, en = ethylenediamine) have been hydrothermally synthesized and structurally characterized. The structures of Ia–d consist of isolated [Ln(dien)3]3+ cations, [Ge2S6]4− anions built up from the connection of two [GeS4] tetrahedra sharing a common edge and Cl− ions. II contains binuclear [Er2(dien)4(μ-OH)2]4+ cations constructed by the linkage of [Er(dien)2]3+ ions and –OH bridging groups, and [Ge2S6]4− anions. III contains neutral holmium-centred complexes, where the unusual protonated tetrahedral anion [GeS3(SH)]3− acts as a chelating ligand to complex the [Ho(en)(trien)]3+ cation. A systematic investigation of six lanthanide thiogermanates and four reported compounds revealed that both the well-known lanthanide contraction and different chelating organic amines have a significant influence on the formation of lanthanide thiogermanates under solvothermal conditions. Density functional theory calculation for III has also been performed and the absorption edges of all compounds have been investigated by UV-vis spectroscopy.

Incorporation of manganese complexes into thioarsenates(V), displaying a new structural motif

Abstract Two new manganese thioarsenates(V) [Mn(Hen)2(AsS4)2]·2(Hen) (1, en = ethylenediamine) and β-{[Mn(dien)2][Mn2(dien)2(AsS4)2] (2, dien = diethyleneamine) have been solvothermally synthesized and structurally characterized. 1 contains [Mn(Hen)2(AsS4)2]2− built from two [AsS4]3− anions bound to [Mn(Hen)2]4+, and two protonated Hen+ cations, which provide a rare example of monoprotonated ethylenediamine as monodentate ligand within chalcogenidoarsenates. 2 contains two conformations of a [Mn2(dien)2(AsS4)2]2− cluster constructed from two [Mn(dien)]2+ groups bridged by two μ-[AsS4]3− anions and charge compensating complex cations [Mn(dien)2]2+. Their optical properties have been characterized by UV–vis spectra and the theoretical band structure of 1 has also been studied.

One-Step Preparation of 1-D Copper(I) Polymer of Pyridyl-Ester with Fluorescence Properties

The reported metal complexes of ethyl isonicotinate (L) and its derivative ligands are usually synthetized by two-step method with difficult synthetic routes, but this work first provides one-step solvothermal method for preparation of 1-D copper(I) coordination polymer of ethyl isonicotinate [CuI(L)]n (1), where 1-D stair-step chain [Cu2I2]n is decorated by L ligand. 1 exhibits a fluorescence emission at room temperature, and its theoretical band structure has also been studied.