A Series of CuII–LnIII Metal–Organic Frameworks Based on 2,2′-Bipyridine-3,3′-dicarboxylic Acid: Syntheses, Structures, and Magnetic Properties

• Published in: Crystal growth & design 2014-12, Vol.14 (12), p.6409-6420
• Main Authors: Liu, Ke, Zhou, Jing-Min, Li, Hui-Min, Xu, Na, Cheng, Peng
• Format: Article
• Language: English
• Subjects: Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; Exact sciences and technology; Materials science; Organic compounds; Other materials; Physics; Specific materials; Structure of solids and liquids; crystallography; Structure of specific crystalline solids
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/cg5012617

A series of CuII–LnIII heterometallic metal–organic frameworks (HMOFs), displaying three types of structures with the formulas of {[Ln2Cu(BDPC)4­(H2O)6]­·9H2O} n (Ln = La, 1; Pr, 2; Nd, 3; BPDC2– = 2,2′-bipyridine-3,3′-dicarboxylate), {[Ln2Cu2(BPDC)5­(H2O)6]­·9H2O} n (Ln = Pr, 4; Nd, 5; Sm, 6; Eu, 7; Gd, 8; Tb, 9) and [DyCu3(BPDC)4­(NO3)­(H2O)6] n (10), have been successfully synthesized and well characterized. Single crystals available for X-ray diffraction measurements were carried out for MOFs 3, 7, 9, and 10. Powder X-ray diffraction and Fourier transform infrared analysis demonstrate the isomorphism for MOFs 1–3, as well as MOFs 4–9. The BPDC2– ligand herein exhibits seven different coordination modes to link metal centers for the construction of different three-dimensional structures. The structures of the three types of CuII-LnIII HMOFs can be described topologically with the Schläfli symbol {3·62}{32·66·73·83·9}­{62·7}, {4·62}2{42·64·86·103}­{6·82}2, and {4·8·9}2­{6·8·9}2­{6·82·93}­{82·9}2, of which the latter two are new topologies. The static magnetic properties of the 10 HMOFs and dynamic magnetic properties of 9-Tb 2 Cu 2 and 10-DyCu 3 have been studied.