Two Types of New Three-Dimensional d–f Heterometallic Coordination Polymers Based on 2‑(Pyridin-3-yl)‑1H‑Imidazole-4,5-Dicarboxylate and Oxalate Ligands: Syntheses, Structures, Luminescence, and Magnetic Properties

• Published in: Crystal growth & design 2012-09, Vol.12 (9), p.4441-4449
• Main Authors: Cai, Song-Liang, Zheng, Sheng-Run, Wen, Zhen-Zhen, Fan, Jun, Wang, Ning, Zhang, Wei-Guang
• Format: Article
• Language: English
• Subjects: Condensed matter: electronic structure, electrical, magnetic, and optical properties; Condensed matter: structure, mechanical and thermal properties; Exact sciences and technology; Optical properties and condensed-matter spectroscopy and other interactions of matter with particles and radiation; Optical properties of bulk materials and thin films; Photoluminescence; Physics; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Thermal expansion; thermomechanical effects and density; Thermal properties of condensed matter; Thermal properties of crystalline solids
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/cg300613t

Two types of new d–f heterometallic coordination frameworks, [Ln2M(μ3-HPyIDC)2(ox)2(H2O)4]·4H2O [Ln = Sm, M = Co (1); Ln = Sm, M = Fe (2); Ln = Eu, M = Co (3); Ln = Eu, M = Fe (4); Ln = Gd, M = Co (5); H3PyIDC = 2-(pyridine-3-yl)-1H-4,5-imidazoledicarboxylic acid; ox = oxalate] for type I and [Ln2Ag3(μ5-PyIDC)(μ6-PyIDC)(μ2-OH)(ox)(H2O)2] [Ln = Sm (6); Gd (7); Tb (8); Dy (9)] for type II, were prepared under hydrothermal conditions and structurally characterized. Complexes 1–5 are isostructural, exhibiting three-dimensional (3D) heterometallic networks with pcu topology based on the linkages of two-dimensional (2D) lanthanide–oxalate layers and pillar-like M(HPyIDC)2 (M = Fe, Co) subunits. Complexes 6–9 are also isomorphous and display another type of 3D heterometallic coordination framework built through the connections of 2D lanthanide–oxalate layers and one-dimensional (1D) Ag2(PyIDC)2 chains. Interestingly, the oxalate ligands in complexes 6–9 are produced by the in situ decarboxylation of the H3PyIDC ligand in the presence of 4,4′-bipyridine (4,4′-bpy). The photoluminescence, thermal stabilities, and magnetic properties of the selected complexes were also investigated.