Investigating metal size effects in the Ln/As/Se/amine (Ln = lanthanide excluding Pm, amine = en, dien, en+trien) systems: solvothermal syntheses and characterizations of lanthanide selenidoarsenatesElectronic supplementary information (ESI) available: IR spectra of 1a and 2a (Fig. S1), structural figures of 1c, 1d, 2a, 3a and 3c (Fig. S2-S7), selected bond lengths and angles for 1a-3c (Table S1-S12). CCDC reference numbers 767669-767680 for 1a-3c. For ESI and crystallographic data in CIF or oth

• Main Authors: Wang, Jiao, Pan, Yingli, Chen, Jiangfang, Gu, Jiansheng, Zhang, Yong, Jia, Dingxian
• Format: Journal Article
• Language: English
• Published: 20.07.2010
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c0dt00040j

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)(μ-η 1 ,η 1 -AsSe 4 )] (Ln = La( 1a ), Ce( 1b ), Nd( 1c )), [Ln(en) 4 ]AsSe 4 ·0.5en (Ln = Sm( 1d ), Gd( 1e ), Dy( 1f )), [Ln(dien) 2 (μ-η 1 ,η 2 -AsSe 4 )] (Ln = La( 2a ), Ce( 2b ), Pr( 2c )), [Ln(en)(trien)(μ-η 1 ,η 2 -AsSe 4 )] (Ln = La( 3a ), Nd( 3b )) and [Sm(en)(trien)(η 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 ] 3− 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. A systematic investigation of Ln/As/Se/en (dien or en+trien) systems across the lanthanide series clarifies the relationship between the structures of lanthanide selenidoarsenates and the lanthanide ion size.