A series of three-dimensional 3d-4f cyanide heterometallic coordination polymers: synthesis, crystal structure, photoluminescent and magnetic propertiesElectronic supplementary information (ESI) available. CCDC 964391-964403. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c3ce42025f

• Main Authors: Ma, Ying-Zhao, Zhang, Li-Min, Peng, Guo, Zhao, Chong-Jian, Dong, Ruo-Ting, Yang, Cheng-Feng, Deng, Hong
• Format: Article
• Language: English
• ISSN: 1466-8033
• DOI: 10.1039/c3ce42025f

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 ]· x H 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 (H 2 O) 6 ]·2H 2 O [Ln = Tb ( II-A ), Ln = Dy ( II-B )], [Ln 2 Cu 2.5 (ina) 3 (F) 2.5 (SO 4 ) 0.5 (CN) 2 (H 2 O) 0.5 ] [Ln = Tb ( III-A ), Ln = Dy ( III-B )], [Ln 3 Cu 4.5 (OH) 2 (ina) 6 (OAc) 2 (CN) 3.5 ]·H 2 O [Ln = Tb ( IV-A ), Ln = Dy ( IV-B )] and [Ln 2 Cu 5. (ina) 6 (OAc)(CN) 4 (H 2 O) 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. Five different types of novel three-dimensional (3D) 3d-4f cyanide heterometallic coordination polymers are synthesized. All the compounds are constructed from cyano-containing copper-inorganic motifs and Ln-containing motifs.