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Cyanido-Bridged Heterometallic Oligonuclear Complexes and Coordination Polymers Constructed Using Tridentate Schiff-Base Ligands: Synthesis, Crystal Structures, and Magnetic and Luminescence Properties. A New Trimeric Water Cluster

Abstract :

Five new Cu-II-Ag-I, Cu-II-Cu-I, and Zn-II-Au-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)(infinity)[{Cu-2(salaepipH)(2)(mu-CN)}{mu-[Ag(CN)(2)]}]-(ClO4)(2)center dot 4H(2)O 2, (1)(infinity)[{(salaepy)-Cu}{mu-[Ag(CN)(2)]}] 3, (1)(infinity)[{(salaepy)-Cu}{mu-[Cu(CN)(2)]}] 4, [(salaepy)Zn-NCAuCN](2)center dot H2O 5. The Schiffbase 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)](-) and CN- ions, resulted from the partial decomposition of the silver complex. The 3-D architecture of the crystal is constructed from 1-D coordination polymers, [{Cu-2(salaepipH)(2)(mu-CN)}{mu-[Ag(CN)(2)]}](n)(2n+), 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)](n)(n-) (M = Ag-I or Cu-I), 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 = -2.8 cm(-1), H = -jS(1)S(2)) 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 = 55.2 cm(-1)). Compound 5 exhibits blue luminescence (lambda = 464 nm, lambda(ex) = 400 nm).

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https://hal.univ-angers.fr/hal-03344537
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Soumis le : mercredi 15 septembre 2021 - 10:10:51
Dernière modification le : jeudi 9 décembre 2021 - 15:46:06

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Catalin Maxim, F. Tuna, Augustin-M. Madalan, Narcis Avarvari, Marius Andruh. Cyanido-Bridged Heterometallic Oligonuclear Complexes and Coordination Polymers Constructed Using Tridentate Schiff-Base Ligands: Synthesis, Crystal Structures, and Magnetic and Luminescence Properties. A New Trimeric Water Cluster. Crystal Growth & Design, American Chemical Society, 2012, 12 (3), pp.1654-1665. ⟨10.1021/cg2016947⟩. ⟨hal-03344537⟩

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