Reference

Double-Stranded Metal-Organic Networks for One-Dimensional Mixed Valence Coordination Polymers

Double-Stranded Metal-Organic Networks for One-Dimensional Mixed Valence Coordination Polymers. Robertson, Daniel; Cannon, John F.; Gerasimchuk, Nikolay ( Department of Chemistry, Southwest Missouri State University, Springfield, MO 65804, USA). Inorganic Chemistry, 44(23), 8326-8342 (English) 2005 American Chemical Society. CODEN: INOCAJ. ISSN: 0020-1669. DOCUMENT TYPE: Journal CA Section: 78 (Inorganic Chemicals and Reactions) Section cross-reference(s): 25, 75 The design of new types of metal-org. networks and the search for unusual crystal architecture represents an important task for modern inorg. and materials chem. research. A group of new monosubstituted phenylcyanoximes, contg. F, Cl, and Br atoms at the 2, 3, or 4 positions, were synthesized using the high yield nitrosation reaction with CH3-ONO and were spectroscopically (1H NMR, 13C NMR, UV-visible, IR, mass spectrometry) and structurally characterized. Results of x-ray anal. revealed nonplanar trans-anti geometry for 2-chlorophenyl(oximino)acetonitrile, H(2Cl-PhCO); a nonplanar anti configuration for 4-chlorophenyl(oximino)acetonitrile, H(4Cl-PhCO); and planar cis-syn geometry for 3-fluorophenyl(oximino)acetonitrile, H(3F-PhCO). All arylcyanoximes undergo deprotonation in solns. with the formation of colored anions exhibiting pronounced neg. solvatochromism in polar protic and aprotic solvents.Several substances like 3215-64-3 may be metioned in this study. Nine Tl(I) cyanoximates were obtained using the reaction between hot (~95°) aq. solns. of Tl2CO3 and solid powdery monohalogenated arylcyanoximes HL. Crystal structures of two Tl(I) cyanoximates [Tl(2Cl-PhCO) and Tl(4Br-PhCO)] contained centrosym. dimeric units (TlL)2 that are connected to a coordination polymer by an O atom of the oxime group of the neighboring mol. Cyanoxime anions act as bridging ligands in both structures where the polymeric motif consists of double-stranded Tl-O chains interconnected with the formation of zigzagging Tl2O2 planar rhombes. Tl atoms form infinite linear arrays with close intermetallic sepns. The nearest Tl(I)×××Tl(I) distances are 3.838 and 4.058 ? in the Tl(2Cl-PhCO) and Tl(4Br-PhCO) structures, resp., close to that in metallic Tl (3.456 ?). Monosubstituted Ph groups are well aligned in p-stacking columns that are perpendicular to the array of Tl(I) atoms and stabilize formed structures. Coordination polyhedrons of Tl(I) in these complexes represent distorted trigonal pyramids with stereoactive lone pair. .