College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People's Republic of China.
Dalton Trans. 2010 Aug 14;39(30):7066-72. doi: 10.1039/c0dt00040j. Epub 2010 Jun 24.
Three solvothermal systems Ln/As/Se/en, Ln/As/Se/dien and Ln/As/Se/(en+trien) (Ln = lanthanide excluding Pm, en = ethylenediamine, dien = diethylenetriamine, trien = triethylenetetramine) were investigated in detail across the lanthanide series, and ternary lanthanide selenidoarsenates [Ln(en)(3)(H(2)O)(mu-eta(1),eta(1)-AsSe(4))] (Ln = La(1a), Ce(1b), Nd(1c)), [Ln(en)(4)]AsSe(4) x 0.5 en (Ln = Sm(1d), Gd(1e), Dy(1f)), [Ln(dien)(2)(mu-eta(1),eta(2)-AsSe(4))] (Ln = La(2a), Ce(2b), Pr(2c)), [Ln(en)(trien)(mu-eta(1),eta(2)-AsSe(4))] (Ln = La(3a), Nd(3b)) and [Sm(en)(trien)(eta(2)-AsSe(4))] (3c) were prepared. Systematic investigations of the three systems clarify the relationship between the molecular structures of the synthetic lanthanide selenidoarsenates and the metal size evolution of the lanthanide series. Meanwhile, the coordination modes of the AsSe(4) tetrahedral anion to the same lanthanide ion are dependent on the denticity of ethylene polyamine as the second ligand. The lanthanide selenidoarsenates exhibit semiconducting properties with E(g) between 2.15 and 2.31 eV.
三个溶剂热体系 Ln/As/Se/en、Ln/As/Se/dien 和 Ln/As/Se/(en+trien)（Ln = 镧系元素，不包括 Pm，en = 乙二胺，dien = 二乙烯三胺，trien = 三乙烯四胺）在镧系元素系列中进行了详细研究，同时还制备了三元镧系硒代砷酸盐 [Ln(en)(3)(H(2)O)(mu-eta(1),eta(1)-AsSe(4))]（Ln = La(1a)、Ce(1b)、Nd(1c)）、[Ln(en)(4)]AsSe(4) x 0.5 en（Ln = Sm(1d)、Gd(1e)、Dy(1f)）、[Ln(dien)(2)(mu-eta(1),eta(2)-AsSe(4))]（Ln = La(2a)、Ce(2b)、Pr(2c)）、[Ln(en)(trien)(mu-eta(1),eta(2)-AsSe(4))]（Ln = La(3a)、Nd(3b)）和 [Sm(en)(trien)(eta(2)-AsSe(4))]（3c）。对这三个体系的系统研究阐明了合成镧系硒代砷酸盐的分子结构与镧系元素系列中金属尺寸演化之间的关系。同时，AsSe(4)四面体阴离子与同一镧系离子的配位模式取决于乙二胺多胺作为第二配体的齿密度。这些镧系硒代砷酸盐具有 2.15 至 2.31eV 之间的半导体性质。
