The first examples of 1-D organic hybrid lanthanoid thioarsenates based on two [(AsS4)-S-V](3). linkage modest

Abstract

A series of new 1-D organic hybrid lanthanoid thioarsenates [Ln(dap)2]2(mu-eta(1):eta(1):eta(1):eta(1)-AsS4)(mu-eta(1):eta(1)-(AsS4)-S-V)]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 [(AsS4)-S-V](3)-linkage modes, namely mu-eta(1):eta(1):eta(1):eta(1)-(AsS4)-S-V and mu-eta(1):eta(1)-(AsS4)-S-V, which are linked alternately with [Ln(dap)2]3+ groups into 1-D neutral chains [Ln(dap)2]2(mu-eta(1):eta(1):eta(1):eta(1)-(AsS4)-S-V)(mu-eta(1):eta(1)-(AsS4)-S-V)]n, which represent the first examples of 1-D organic hybrid lanthanoid thioarsenates based on two [(AsS4)-S-V]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)S(4)] [Ln = Tb (IIa), Dy (IIb), Ho (IIIc), and Er (IIId)] and [Er(dien)2As(V)S(4)] (III, dien = diethylenetriamine) are also provided. Both II and III contain neutral lanthanide-centred complexes, where the tetrahedral anion [(AsS4)-S-V](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.