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

Abstract

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 [Ln3Cu7(ina)8(OAc)2(CN)6]·xH2O [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], [Ln2Cu6.5(ina)7(Cl)3(CN)2.5(H2O)6]·2H2O [Ln = Tb (II-A), Ln = Dy (II-B)], [Ln2Cu2.5(ina)3(F)2.5(SO4)0.5(CN)2(H2O)0.5] [Ln = Tb (III-A), Ln = Dy (III-B)], [Ln3Cu4.5(OH)2(ina)6(OAc)2(CN)3.5]·H2O [Ln = Tb (IV-A), Ln = Dy (IV-B)] and [Ln2Cu5.(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)}∞ 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)}∞ 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.