title: Synthesis, structures, and magnetic behavior of a series of copper(II) azide polymers of Cu4 building clusters and isolation of a new hemiaminal ether as the metal complex.
abstract: Four new neutral copper azido polymers, [Cu(4)(N(3))(8)(L(1))(2)](n) (1), [Cu(4)(N(3))(8)(L(2))(2)](n) (2), [Cu(4)(N(3))(8)(L(3))(2)](n) (3), and [Cu(9)(N(3))(18)(L(4))(4)](n) (4) [L(1-4) are formed in situ by reacting pyridine-2-carboxaldehyde with 2-[2-(methylamino)ethyl]pyridine (mapy, L(1)), N,N-dimethylethylenediamine (N,N-dmen, L(2)), N,N-diethylethylenediamine (N,N-deen, L(3)), and N,N,2,2-tetramethylpropanediamine (N,N,2,2-tmpn, L(4))], have been synthesized by using 0.5 mol equiv of the chelating tridentate ligands with Cu(NO(3))(2)·3H(2)O and an excess of NaN(3). Single-crystal X-ray structures show that the basic unit of these complexes, especially 1-3, contains very similar Cu(II)(4) building blocks. The overall structure of 3 is two-dimensional, while the other three complexes are one-dimensional in nature. Complex 1 represents a unique example containing hemiaminal ether arrested by copper(II). Complexes 1 and 2 have a rare bridging azido pathway: both end-on and end-to-end bridging azides between a pair of Cu(II) centers. Cryomagnetic susceptibility measurements over a wide range of temperature exhibit dominant ferromagnetic behavior in all four complexes. Density functional theory calculations (B3LYP functional) have been performed on complexes 1-3 to provide a qualitative theoretical interpretation of their overall ferromagnetic behavior.
authors.affiliation: Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012, India.
authors.forename: Sandip
authors.initials: S
authors.lastname: Mukherjee
authors.forename: Bappaditya
authors.initials: B
authors.lastname: Gole
authors.forename: You
authors.initials: Y
authors.lastname: Song
authors.forename: Partha Sarathi
authors.initials: PS
authors.lastname: Mukherjee
mesh_terms: D001386:Azides / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D004987:Ethers / Q000737:chemistry*; D060526:Magnetic Fields; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry
chemical_list: D001386:Azides; D004987:Ethers; D009942:Organometallic Compounds; D011108:Polymers; D003300:Copper