Cyanido-Bridged Heterometallic Oligonuclear Complexes and Coordination Polymers Constructed Using Tridentate Schiff-Base Ligands: Synthesis, Crystal Structures, and Magnetic and Luminescence Propertie

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• 作者：Catalin Maxim ; Floriana Tuna ; Augustin M. Madalan ; Narcis Avarvari ; Marius Andruh
• 刊名：Crystal Growth & Design
• 出版年：2012
• 出版时间：March 7, 2012
• 年：2012
• 卷：12
• 期：3
• 页码：1654-1665
• 全文大小：758K
• 年卷期：v.12,no.3(March 7, 2012)
• ISSN：1528-7505

文摘

Five new Cu^II鈥揂g^I, Cu^II鈥揅u^I, and Zn^II鈥揂u^I complexes have been obtained starting from copper(II) and, respectively, zinc(II) complexes with (NNO) Schiff-base ligands: [{(H₂O)(saldmen)Cu}{(NC)Ag(CN)}] 1, ¹_{鈭?/sub>[{Cu2(salaepipH)2(渭-CN)}{渭-[Ag(CN)2]}](ClO4)2路4H2O 2, ¹鈭?/sub>[{(salaepy)Cu}{渭-[Ag(CN)2]}] 3, ¹鈭?/sub>[{(salaepy)Cu}{渭-[Cu(CN)2]}] 4, [(salaepy)Zn-NCAuCN]2路H2O 5. The Schiff-base ligands (Hsaldmen, Hsalaepip, Hsalaepy) have been obtained by reacting the salicylaldehyde with N,N-dimethyletylenediamine, N-(2-aminoethyl)piperazine, and, respectively, 2-(2-aminoethyl)-pyridine. The structures of compounds 1 and 5 consist of discrete bi- and, respectively, tetranuclear species. The analysis of the packing diagram for crystal 1 reveals the formation of supramolecular double chains sustained by hydrogen-bond interactions involving the aqua ligand. Compounds 2, 3, and 4 are one-dimensional coordination polymers. The structure of 2 consists of chains constructed from {Cu(salaepip)} nodes bridged alternatively by [Ag(CN)2]^{鈭?/sup> and CN鈥?/sup> ions, resulted from the partial decomposition of the silver complex. The 3-D architecture of the crystal is constructed from 1-D coordination polymers, [{Cu2(salaepipH)2(渭-CN)}{渭-[Ag(CN)2]}]n2n+, which are connected by three water molecules that form a triangular water cluster, resulting in a scaffold-like structure with large channels. Compounds 3 and 4 are similar. Their structures can be described as resulting from zigzag anionic chains, [M(CN)2]nn鈥?/sup> (M = AgI or CuI), with three-coordinated silver(I) or copper(I) ions, to which monocationic complexes, {(salaepy)Cu}, are attached. The cryomagnetic properties of compounds 1 and 2 have been investigated. Weak antiferromagnetic interactions (J = 鈭?.8 cm鈥?, H = 鈥?i>JS1S2) mediated by hydrogen bonds are observed for compound 1. The cyanido bridge connecting the basal coordination sites of two copper(II) ions in 2 mediates a moderate antiferromagnetic coupling (J = 鈭?5.2 cm鈥?). Compound 5 exhibits blue luminescence (位 = 464 nm, 位ex = 400 nm).}}