A Quasi-Intramolecular Solid-Phase Redox Reaction of Ammonia Ligands and Perchlorate Anion in Diamminesilver(I) Perchlorate

The reaction of ammoniacal AgNO3 solution (or aq. solution of [Ag(NH3)2]NO3) with aq. NaClO4 resulted in [Ag(NH3)2]ClO4 (compound 1). Detailed spectroscopic (correlation analysis, IR, Raman, and UV) analyses were performed on [Ag(NH3)2]ClO4. The temperature and enthalpy of phase change for compound 1 were determined to be 225.7 K and 103.04 kJ/mol, respectively. We found the thermal decomposition of [Ag(NH3)2]ClO4 involves a solid-phase quasi-intramolecular redox reaction between the perchlorate anion and ammonia ligand, resulting in lower valence chlorine oxyacid (chlorite, chlorate) components. We did not detect thermal ammonia loss during the formation of AgClO4. However, a redox reaction between the ammonia and perchlorate ion resulted in intermediates containing chlorate/chlorite, which disproportionated (either in the solid phase or in aqueous solutions after the dissolution of these decomposition intermediates in water) into AgCl and silver perchlorate. We propose that the solid phase AgCl-AgClO4 mixture eutectically melts, and the resulting AgClO4 decomposes in this melt into AgCl and O2. Thus, the final product of decomposition is AgCl, N2, and H2O. The intermediate (chlorite, chlorate) phases were identified by IR, XPS, and titrimetric methods.

Correlation of the rates of solvolysis of α-bromoisobutyrophenone using both simple and extended forms of the Grunwald-Winstein equation and the application of correlation analysis to related studies

A Grunwald-Winstein treatment of the specific rates of solvolysis of α-bromoisobutyro phenone in 100% methanol and in several aqueous ethanol, methanol, acetone, 2,2,2-trifluoroethanol (TFE), and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) mixtures gives a good logarithmic correlation against a linear combination of NT (solvent nucleophilicity) and YBr (solvent ionizing power) values. The l and m sensitivity values are compared to those previously reported for α-bromoacetophenone and to those obtained from parallel treatments of literature specific rate values for the solvolyses of several tertiary mesylates containing a C(=O)R group attached at the α-carbon. Kinetic data obtained earlier by Pasto and Sevenair for the solvolyses of the same substrate in 75% aqueous ethanol (by weight) in the presence of silver perchlorate and perchloric acid are analysed using multiple regression analysis.

Synthesis, Structure and Properties of Lanthanide-Organic Frameworks with Imidazolylmethylisophthalate Ligands

Three new lanthanide-organic frameworks {[Ln(L)(OClO3)(H2O)]·0.5H2O}n [Ln=Sm (1), Eu (2), Er (3)] have been prepared by hydrothermal reactions of the corresponding lanthanide oxide (Ln2O3), silver perchlorate (AgClO4) and 5-(imidazol-1-ylmethyl)isophthalic acid. The complexes have been characterized by single-crystal and powder X-ray diffraction, IR spectroscopy, and elemental analyses. In 1-3, the metal centers are eight-coordinated to show polyhedral coordination geometries with an LnO8 donor set. The imidazolyl groups are free of coordination, and the perchlorate and carboxylate groups bridge the Ln3+ cations leading to the formation of wave-like layer structures containing metal-chains. The fluorescence properties of complex 2 were investigated.

A one-dimensional silver(I) coordination polymer based on the 2-[2-(pyridin-4-yl)-1H-benzimidazol-1-ylmethyl]phenol ligand exhibiting photoluminescence

A one-dimensional AgIcoordination complex,catena-poly[[silver(I)-μ-{2-[2-(pyridin-4-yl)-1H-benzimidazol-1-ylmethyl]phenol-κ2N2:N3}] perchlorate monohydrate], {[Ag(C19H15N3O)]ClO4·H2O}n, was synthesized by the reaction of 2-[2-(pyridin-4-yl)-1H-benzimidazol-1-ylmethyl]phenol (L) with silver perchlorate. In the complex, theLligands are arranged alternately and link AgIcations through one benzimidazole N atom and the N atom of the pyridine ring, leading to an extended zigzag chain structure. In addition, the one-dimensional chains are extended into a three-dimensional supramolecular architectureviaO—H...O hydrogen-bond interactions and π–π stacking interactions. The complex exhibits photoluminescence in acetonitrile solution, with an emission maximum at 390 nm, and investigation of the thermal stability reveals that the network structure is stable up to 650 K.