title: New 1-D and 3-D thiocyanatocadmates modified by various amine molecules and Cl(-)/CH3COO(-) ions: synthesis, structural characterization, thermal behavior and photoluminescence properties.
abstract: Under ambient conditions, reactions of CdCl2/Cd(CH3COO)2, SCN(-) and various organic amine molecules in strongly acidic solutions afforded the five new thiocyanatocadmates [H2(abpy)][CdCl2(SCN)2] (abpy = azobispyridine) 1, [H(apy)][Cd(SCN)3] (apy = 4-aminopyridine) 2, [H(ba)]2[CdCl2(SCN)2] (ba = tert-butylamine) 3, [H2(tmen)][Cd3Cl6(SCN)2] (tmen = N,N,N',N'-tetramethylethylenediamine) 4, and [H(dba)]2[Cd2(CH3COO)2(SCN)4] (dba = dibutylamine) 5. In compound 2 only, the CH3COO(-) ions in Cd(CH3COO)2 were completely displaced by SCN(-), producing a chained thiocyanatocadmate [Cd(SCN)3](-). In the other four compounds, the Cl(-) or CH3COO(-) ions appeared in the final inorganic anion frameworks. In compound 1, the Cl(-) ions doubly bridge the Cd(2+) centers, forming a one-dimensional (1-D) infinite chain, and the SCN(-) group exists in a terminal form, whereas in compound 3, the reverse situation is observed. Due to a trans-mode arrangement for two terminal Cl(-) or SCN(-) ions around each Cd(2+) center, the inorganic anion chains in compounds 1 and 3 both show a linear shape. In compound 4, Cd(2+) and Cl(-) first aggregate to form a 1-D endless chain with a composition of Cd3Cl6, which can be described as a linear arrangement of the open double cubanes. SCN(-) serves as the second connector, propagating the Cd3Cl6 chain into a three-dimensional (3-D) network with the occluded H2(tmen)(2+) cations. In compound 5, the SCN(-) groups doubly bridge the Cd(2+) centers, forming a 1-D zigzag-shape chain. The formation of the zigzag chain likely derives from chelation of the CH3COO(-) group to the Cd(2+) center. The thermal behavior and the photoluminescence properties of the title compounds were also investigated.
authors: College of Chemistry, State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, Jilin 130012, China. jhyu@jlu.edu.cn xjq@mail.jlu.edu.cn.
authors: Bing
authors: B
authors: Guo
authors: Xiao
authors: X
authors: Zhang
authors: Yan-Ning
authors: YN
authors: Wang
authors: Jing-Jing
authors: JJ
authors: Huang
authors: Jie-Hui
authors: JH
authors: Yu
authors: Ji-Qing
authors: JQ
authors: Xu