SIMULTANEOUS POLYMERIZATION AND FORMATION OF POLYPHENYLACETYLENE FILMS BY RARE-EARTH COORDINATION CATALYSIS Ⅳ.KINETICS AND MECHANISM OF POLYMERIZATION

The CO_2 quenching method has been used for the first time to determine the active complex concen- tration in Nd(naph)_3-Al(i-Bu)_3 catalyst system for polymerization of phenylacetylene into polyphenylacetylene(PPA)films.The kinetics and mechanism of this polymerization have been investigated by CO_2 quenching and IR,UV analytical methods.The kinetic equation can be expressed as Rp=k[M][Cp],and the apparent activation energy is about 13.6 kJ/mol.There is self-termination of chain propagating.Models for formation of the active complex and polymerization mechanism are proposed.

Syntheses,Structures,Fluorescence and Heterogeneous Catalysis of Coordination Polymers with 4-Benzoimidazol-1-yl-methyl Benzoic Acid and 2,2′-Dipyridine

Two coordination polymers called [Ni（L）2]n（1） and [Ni（2,2？-bpy）22（H2O）]n （2）（HL = 4-benzoimidazol-1-yl-methyl benzoic acid, 2,2？-bpy = 2,2＇-dipyridine） were synthesized by solvothermal reaction simultaneously and characterized by elemental analyses, thermogravimetric analysis, X-ray powder diffraction, IR spectroscopy and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in monoclinic system, space group P21/c with a = 14.673（3）, b = 10.773（2）, c = 16.566（3） ？, V = 2559.2（8） A^3, Z = 4 and F（000） = 1160. 2 also crystallizes in monoclinic system, space group C2/c with a = 15.404（3）, b = 12.652（3）, c = 6.5362（13） ？, V = 1246.2（5） A^3, Z = 4 and F（000） = 712. The bridging L ligand connects the Ni^Ⅱ cations into a 2D network in complex 1, while 2 shows a 1D structure formed through the two O atoms of SO4^（2-） ions connecting the molecule. The catalytic properties indicate that complex 1 shows good catalytic activities for the cyanosilylation of 4-chlorobenzaldehyde. In addition, fluorescence property of complex 1 which quenches the excitation intensity in solid state was investigated at room temperature.

Iron species activating chlorite:Neglected selective oxidation for water treatment

Chlorite(ClO_(2)-)is the by-product of the water treatment process carried out using chlorine dioxide(ClO_(2))as an effective disinfectant and oxidant;however,the reactivation of ClO_(2)
has commonly been overlooked.Herein,it was unprecedentedly found that ClO_(2)
could be activated by iron species(Feb:Fe0,FeII,or FeIII),which contributed to the synchronous removal of ClO_(2)
and selective oxidative treatment of organic contaminants.However,the above-mentioned activation process presented intensive Ht-dependent reactivity.The introduction of Feb significantly shortened the autocatalysis process via the accumulation of Cl
or ClO
during the protonation of ClO_(2)
driven by ultrasonic field.Furthermore,it was found that the interdependent high-valent-Fe-oxo and ClO_(2),after identification,were the dominant active species for accelerating the oxidation process.Accordingly,the unified mechanisms based on coordination catalysis([FeN(H_(2)O)a(ClOxm)b]nt-P)were putative,and this process was thus used to account for the pollutant removal by the Feb-activated protonated ClO_(2).This study pioneers the activation of ClO_(2)
for water treatment and provides a novel strategy for“waste treating waste”.Derivatively,this activation process further provides the preparation methods for sulfones and ClO_(2),including the oriented oxidation of sulfoxides to sulfones and the production of ClO_(2) for on-site use.