Copper(I) cyanide networks: synthesis, luminescence behavior and thermal analysis. Part 1. Diimine ligands.
Metal-organic networks of CuCN with diimines (L) = pyrazine (Pyz), 2-aminopyrazine (PyzNH(2)), quinoxaline (Qox), phenazine (Phz), 4,4'-bipyridyl (Bpy), pyrimidine (Pym), 2-aminopyrimidine (PymNH(2)), 2,4-diaminopyrimidine (Pym(NH(2))(2)), 2,4,6-triaminopyrimidine (Pym(NH(2))(3)), quinazoline (Qnz), pyridazine (Pdz), and phthalazine (Ptz) were studied. Open reflux reactions produced complexes (CuCN)(2)(L) for L = Qox, Phz, Bpy, PymNH(2), Pym(NH(2))(2), Qnz, and Pdz and (CuCN)(3)(L) complexes for L = Pyz, PyzNH(2), Qox, Bpy, Pym(NH(2))(3), and Pdz. Also produced were (CuCN)(3)(Pyz)(2), (CuCN)(PyzNH(2)), (CuCN)7(Pym)(2), (CuCN)(5)(Qnz)(2) and (CuCN)(5)(Ptz)(2). X-ray structures are presented for (CuCN)(2)(Pdz), (CuCN)(2)(PymNH(2)), and (CuCN)(7)(Pym)(2). Hydrothermal reactions yielded additional X-ray structures of (CuCN)(2)(PyzNH(2)), (CuCN)(3)(Pym(NH(2))(2)), (CuCN)(4)(Qnz), a second (CuCN)(2)(Pdz) phase, (CuCN)(5)(Pdz)2, (CuCN)(2)(Ptz), and (CuCN)(7)(Ptz)2. Structural trends, including cuprophilic interactions and cyano-bridged Cu(2)(CN)(2) dimer formation, are discussed. Particularly short Cu...Cu interactions are noted for the novel 4- and 5-coordinate Cu(2)(CN)(2) dimers. Thermal analyses show that most of the complexes decompose with loss of L around 160-180 degrees C. Luminescence behavior is relatively weak in the products.
Tronic
Tristan A
TA
Department of Chemistry, College of William and Mary, Williamsburg, Virginia 23187-8795, USA.
deKrafft
Kathryn E
KE
Lim
Mi Jung
MJ
Ley
Amanda N
AN
Pike
Robert D
RD
D002621:Chemistry / Q000379:methods; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray / Q000379:methods; D003486:Cyanides / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D008024:Ligands; D049449:Luminescence; D008956:Models, Chemical; D008968:Molecular Conformation; D011108:Polymers / Q000737:chemistry; D011208:Powders; D014961:X-Ray Diffraction
D003486:Cyanides; D007097:Imines; D008024:Ligands; D011108:Polymers; D011208:Powders; D003300:Copper