Synthesis and Magnetic Properties of Dual-Ligand Divalent Copper Coordination Polymers with Rhomboid Layer, Archimedean Grid, and Self-Penetrated Network Topologies

• Published in: Crystal growth & design Vol. 10; no. 1; pp. 335 - 343
• Main Authors: Sposato, Laura K, Nettleman, Joseph H, Braverman, Maxwell A, Supkowski, Ronald M, LaDuca, Robert L
• Format: Journal Article
• Language: English
• Published: Washington,DC American Chemical Society 06.01.2010
• Subjects: Condensed matter: electronic structure, electrical, magnetic, and optical properties; Condensed matter: structure, mechanical and thermal properties; Exact sciences and technology; Magnetic properties and materials; Organic compounds; Other ferromagnetic metals and alloys; Physics; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Studies of specific magnetic materials; Piperazines; Molecular structure; Polychelate; Ferromagnetic materials; Nitrates; XRD; Topology; Pyridyl radicals; Monocrystals; Hydrogen bonds; Supramolecular structure; Counterions; Ligands; Vanadium oxide; Copper; Magnetic properties; Crystal structure
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/cg900937e

Four divalent copper coordination polymers containing both 1,2-phenylenediacetate (1,2-phda) and dipyridyl-type coligands have been prepared and structurally characterized by single-crystal X-ray diffraction. {[Cu(1,2-phda)(dpa)]·H2O} n (1, dpa = 4,4′-dipyridylamine) possesses a simple (4,4) rhomboid polymeric grid structure but can be considered a (4,6)-connected binodal supramolecular lattice with (4462)(446108) fsc topology. Use of a longer dipyridyl ligand afforded [Cu2(1,2-phda)2(dpp)] n (2, dpp = 1,3-di(4-pyridyl)propane), which manifests a rare self-penetrated rob lattice (48668 topology) built from the linkage of copper dicarboxylate layers through crossed dpp tethers. [Cu(1,2-phda)(H2O)(4-bpmp)0.5] n (3, 4-bpmp = bis(4-pyridylmethyl)piperazine) forms a 5-connected Archimedean cem layer with 334453 topology. The topology of 3 can be alternately described as a 3,4-connected binodal layer with a V2O5-type network. Incorporation of nitrate counterions led to formation of {[Cu(1,2-phda)(H2O)(H4-bpmp)] (NO3)·4.5H2O} n (4), a layered coordination polymer with hydrogen-bonded water molecule/nitrate ion chain motifs situated in the interlamellar regions. Strong antiferromagnetic coupling (J = −278(3) cm−1 with g = 2.28(1)) was observed within the {Cu2(OCO)4} “paddlewheels” in 2, while weak ferromagnetic superexchange (J = 3.5(9) cm−1 with g = 2.12(4)) along the {Cu(OCO)} n was evident in 3.