A series of three-dimensional 3d-4f cyanide heterometallic coordination polymers: Synthesis, crystal structure, photoluminescent and magnetic properties

By the control of experimental parameters such as anions, pH value and reaction temperature, five different types of three-dimensional (3D) 3d-4f cyanide heterometallic coordination polymers (HCPs), namely [Ln(3)Cu(7)(ina)(8)(OAc)(2)(CN)(6)]center dot xH(2)O [x = 0, Ln = Nd (I-A); x = 1, Ln = Eu (I-B), Ln = Gd (I-C), Ln = Tb (I-D), Ln = Dy (I-E), ina = isonicotinate, OAc = acetate], [Ln(2)Cu(6.5)(ina)(7)(Cl)(3)(CN)(2.5)(H2O)(6)]center dot 2H(2)O [Ln = Tb (II-A), Ln = Dy (II-B)], [Ln(2)Cu(2.5)(ina)(3)(F)(2.5)(SO4)(0.5)(CN)(2)(H2O)(0.5)] [Ln = Tb (III-A), Ln = Dy (III-B)], [Ln(3)Cu(4.5)(OH)(2)(ina)(6)(OAc)(2)(CN)(3.5)]center dot H2O [Ln = Tb (IV-A), Ln = Dy (IV-B)] and [Ln(2)Cu(5)(ina)(6)(OAc)(CN)(4)(H2O)(2)] [Ln = Tb (V-A), Ln = Dy (V-B)] have been hydrothermally synthesized and structurally characterized. All the compounds are constructed from cyano-containing copper-inorganic motifs and Ln-containing motifs. In the type I structures, the copper-inorganic motifs can be viewed as double-stranded {Cu(CN)}(infinity) ribbons with projecting sidearms, and the Ln-organic motifs are zigzag chains. In the type II structures, the copper-inorganic motifs are two-dimensional (2D) {CuCl(CN)}(infinity) layers, while the Ln-organic motifs can be described as two kinds of very similar one-dimensional (1D) chains possessing a parallel and alternating arrangement. In type III structures, the copper-inorganic motifs are 2D layers whereas the Ln-organic/inorganic motifs are fluoride-bridging 2D layers. In the type IV structures, the copper-inorganic motifs contain two unique types of 0D copper-cyanide units, while the Ln-organic counterparts are 1D chain structures linked by OH- groups. In type V structures, the copper-inorganic motifs and the Ln-organic motifs are 2D layers that can both be topologically simplified to (4, 4) networks. Moreover, the photoluminescence of I-A, I-B, I-D, II-A, III-A, IV-A and V-A, and the magnetism of I-E, II-B, III-B, IV-B and V-B were investigated.