Conducting polymer wires in mesopore hosts

Nanometer-size conducting structures are of great interest in view of fundamental issues and potential applications. We explore the inclusion chemistry of conjugated polymers and graphite-like materials as a means to create such structures. Novel mesoporous materials with pore diameters in the 3 nm range (MCM-41) are used as hosts. Monomer molecules are introduced via vapor or solution transfer and polymerized either by included or external reagents. The properties of the conjugated systems are studied while encapsulated or after dissolution of the host. In the case of polyaniline formed on oxidation of aniline with persulfate, microwave absorption shows the presence of conducting filaments in the host channels. The above systems are compared with graphite-type material encapsulated in MCM-41 by first forming a precursor polymer such as polyacrylonitrile that is pyrolyzed at 500-800°C. These polymer chains are the first nanometer-size conducting filaments stabilized in a well-defined channel host

Electrochemical study of 1,3-indandione derivatives of terthiophenes

Properties and behavior of a group of four newly synthesized derivatives of terthiophene and terthienylenvinylene was studied. All four investigated monomers bear a 1,3-indandione substituent at the central thiophene ring and two of them (ThIV, ThIVM) have additional vinyl bonds introduced between the thiophene rings. In addition, ThIM and ThIVM have 5 positions of the two terminal rings blocked with methyl groups. The measurements were done using cyclic voltamperometry (CV) in solutions of 0.1M Bu4NBF4 in CH2Cl2. It was found that ThI and ThIV polymerise easily. CV of ThI reveals a reduction peak resulting probably from the abstraction of a proton. During polymerisation of ThIV a group of peaks is observed indicating its stepwise oxidation process. The polymerisation potential of ThIV was found to be lower than that of ThI which could mean that formation of radical-cation is easier in the former. Stability measurements indicated that polymer films of ThI are electrochemically stable in CH2Cl2 and films of ThIV are not. Efforts to polymerise ThIM and ThIVM failed. Their CVs revealed only peaks coming from oxidation of the monomers, some of which were semi-reversible

Overriding Default Calling Context In Javascript

The article is devoted to overriding the context of function calls in JavaScript. Let's consider all possible cases of setting the context of functions. We will analyze how effective the existing mechanisms are. As a result, an alternative way to set the context of functions will be formulated

Electrochemistry and spectroelectrochemistry of polymers based on D-A-D and D-D-D bis( N -carbazolyl) monomers, effect of the donor/acceptor core on their properties

In this work we present electropolymerization of monomers of an unusual type using N-linked carbazole units to limit their conjugation. The polymers thus obtained have limited conjugation through the backbone. Using donor-acceptor-donor (D-A-D) and donor-donor-donor (D-D-D) monomers we evaluate the effects of the presence (or absence) of charge transfer states on synthesized electropolymers. The use of a D-A-D monomer resulted in obtaining an ambipolar polymer with quasi-reversible reduction

Electrochemical and optical aspects of cobalt meso-carbazole substituted porphyrin complexes

A series of cobalt (II) porphyrin complexes modified with carbazole rings at one or more meso positions of the macrocycle were synthesized and characterized as to their spectroscopic and basic electrochemical properties in non-aqueous media. The effect of the number and position (syn and anti) of carbazole groups on the complexes properties were investigated. The comparison was made to cobalt (II) porphyrin containing mesityl groups at the meso-positions. The relation between the site of redox processes in cobalt meso-carbazole substituted porphyrins were analysed. It was shown that the conjugated π-ring system of the porphyrin macrocycle, the cobalt central metal ion and the carbazole peripheral substituents are redox-active

Consequence of one-electron oxidation and one-electron reduction for aniline

Quantum-chemical calculations were performed for all possible isomers of neutral aniline and its redox forms, and intramolecular proton-transfer (prototropy) accompanied by π-electron delocalization was analyzed. One-electron oxidation (PhNH2 – e → [PhNH2]+•) has no important effect on tautomeric preferences. The enamine tautomer is preferred for oxidized aniline similarly as for the neutral molecule. Dramatical changes take place when proceeding from neutral to reduced aniline. One-electron reduction (PhNH2 + e → [PhNH2]-•) favors the imine tautomer. Independently on the state of oxidation, π- and n-electrons are more delocalized for the enamine than imine tautomers. The change of the tautomeric preferences for reduced aniline may partially explain the origin of the CH tautomers for reduced nucleobases (cytosine, adenine, and guanine)