The first examples of 1-D organic hybrid lanthanoid thioarsenates based on two [As(V)S4](3-) linkage modes.

ABSTRACT

A series of new 1-D organic hybrid lanthanoid thioarsenates [Ln(dap)2]2(µ-η(1)η(1)η(1)η(1)-AsS4)(µ-η(1)η(1)-As(V)S4)]n {Ln = Ce (Ia), Pr (Ib), Nd (Ic), and Sm (Id); dap = diaminopropane} have been prepared under solvothermal conditions and structurally characterized. Compounds Ia-d contain two [As(V)S4](3-) linkage modes, namely µ-η(1)η(1)η(1)η(1)-As(V)S4 and µ-η(1)η(1)-As(V)S4, which are linked alternately with [Ln(dap)2](3+) groups into 1-D neutral chains [Ln(dap)2]2(µ-η(1)η(1)η(1)η(1)-As(V)S4)(µ-η(1)η(1)-As(V)S4)]n, which represent the first examples of 1-D organic hybrid lanthanoid thioarsenates based on two [As(V)S4](3-) linkage modes. To learn more about the influence of lanthanide contraction on the formation of lanthanoid thioarsenates, five organic hybrid lanthanoid thioarsenates [Ln(dap)3As(V)S4] [Ln = Tb (IIa), Dy (IIb), Ho (IIIc), and Er (IIId)] and [Er(dien)2As(V)S4] (III, dien = diethylenetriamine) are also provided. Both II and III contain neutral lanthanide-centred complexes, where the tetrahedral anion [As(V)S4](3-) acts as a chelating ligand to the complex [Ln(dap)3](3+)/[Er(dien)2](3+) cation. Their optical properties have been characterized by UV-vis spectra, and the density functional theory calculation of Ia has been performed.