Chelating and bridging bis(diphenylphosphino)aniline complexes of copper(I)

The ligand bis(diphenylphosphino)aniline (dppan) has been shown to be a versatile ligand sporting different coordination modes and geometries as dictated by copper(I) and the counter ion. The molecular structures of its Cu(I) complexes were characterized by X-ray crystallography. The ligand was found in a chelating mode and monomeric complexes were formed when the ligand to copper ratio was 2: 1 and the anion was non-coordinating. However, with thiocyanate as the counter anion, the ligand was found to adopt two different modes, with one ligand chelating and the other acting as a monodentate ligand. With CuX (X = Cl, Br), dppan formed a tetrameric complex when the ligand and metal were reacted in the ratio of 1:1. But reactions containing ligand and metal in the ratios of 1: 2 or 2: 1, resulted in the formation of a mixture of species in solution. Crystallization however, led to the isolation of the tetrameric complex. Variable temperature P-31{H-1} NMR spectra of the isolated tetramers did not show the presence of chelated structures in solution. Tetra-alkylammonium salts were added to solutions of various complexes of dppan and studied by P-31{H-1} NMR to probe the effect of anions on the stability of complexes in solution. The Cu-dppan complexes were robust and did not interconvert with other structures in solution unlike the bis(diphenylphosphino) isopropylamine complexes. (C) 2011 Elsevier B.V. All rights reserved.

Probing the limits of steric constraints in the oligomerization of copper(I) complexes: structures of two sterically congested oligomers

Oligomeric copper(I) clusters are formed by the insertion reaction of copper(I) aryloxides into heterocumulenes. The effect of varying the steric demands of the heterocumulene and the aryloxy group on the nuclearity of the oligomers formed has been probed. Reactions with copper(I)2-methoxyphenoxide and copper(I)2-methylphenoxide with PhNCS result in the formation of hexameric complexes hexakis[N-phenylimino(aryloxy)methanethiolato copper(I)] 3 and 4 respectively. Single crystal X-ray data confirmed the structure of 3. Similar insertion reactions of CS2 with the copper(I) aryloxides formed by 2,6-di-tert-butyl-4-methylphenol and 2,6-dimethylphenol result in oligomeric copper(I) complexes 7 and 8 having the (aryloxy)thioxanthate ligand. Complex 7 was confirmed to be a tetramer from single crystal X-ray crystallography. Reactions carried out with 2-mercaptopyrimidine, which has ligating properties similar to N-alkylimino(aryloxy)methanethiolate, result in the formation of an insoluble polymeric complex 11. The fluorescence spectra of oligomeric complexes are helpful in determining their nuclearity. Ir has been shown that a decrease in the steric requirements of either the heterocumulene or aryloxy parts of the ligand can compensate for steric constraints acid facilitate oligomerization. (C) 1999 Elsevier Science Ltd. All rights reserved.

Synthesis and characterization of novel charge transfer complexes formed by N,N%-bis(ferrocenylmethylidene)-p-phenylenediamine and N-(ferrocenylmethylidene)aniline

N,N'-Bis(ferrocenylmethylidene)-p-phenylenediamine 1 and N-(ferrocenylmethylidene) aniline 2 are readily synthesized by Schiff base condensation of appropriate units. Iodine (I-2), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), tetrachloro-1,4-benzoquinone (CA), tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) form charge transfer complexes with 1 and 2. IR spectroscopy suggests an increase in the amount of charge transferred from the ferrocenyl ring to the oxidant in the order, I-2 < CA < TCNQ < TCNE approximate to DDQ. EPR spectra of the oxidized binuclear complexes are indicative of localized species containing iron- and carbon-centered radicals. The Mossbauer spectrum of the iodine oxidized complex of 1 reveals the presence of both Fe(III) and Fe(II) centers. Variable temperature magnetic and Mossbauer studies show that the ratio of Fe(III)/Fe(II) centers varies as a function of temperature. The larger Fe(II)/Fe(III) ratio at lower temperatures is best explained by a retro charge transfer from the iodide to the iron(III) metal center. There is negligible solvent effect on the formation of the iodine oxidized charge transfer complex of 1. (C) 1999 Elsevier Science S.A. All rights reserved.

Effect of the sulfonic acid group on copolymers of aniline and toluidine with m-aminobenzene sulfonic acid

This article describes the results of the preparation and characterization of self-doped conducting copolymers of aniline and toluidine with m-aminobenzene sulfonic acid. The copolymers have an intrinsic acid group that is capable of doping polyaniline. Spectroscopic, morphological, and electrical conductivity studies have provided insight into the structural and electronic properties of the copolymers. The differences in the properties of polyaniline and polytoluidine due to the sulfonic acid ring substituent on the phenyl ring are discussed. The scanning electron micrographs of the copolymers reveal regions of sharp-edged, needle-shaped structures, whereas the X-ray diffraction patterns show that the copolymers are relatively more crystalline in nature. (C) 2002 Wiley Periodicals, Inc.

Synthesis of electrically conducting copolymers of aniline with o/m-amino benzoic acid by an inverse emulsion pathway

Copolymers of aniline and ortholmeta-amino benzoic acid were synthesized by chemical polymerization using an inverse emulsion pathway. The copolymers are soluble in organic solvents, and the solubility increases with the amino benzoic acid content in the feed. The reaction conditions were optimized with emphasis on high yield and relatively good conductivity (2.5 X 10(-1) S cm(-1)). The copolymers were characterized by a number of techniques including UV-vis, FT-IR, FT-Raman, EPR and NNM spectroscopy, thermal analysis, SEM and conductivity. The influence of the carboxylic acid group ring substituent on the copolymers is investigated. The spectral studies reveal that the amino benzoic acid groups restrict the conjugation along the polymer chain. The SEM micrographs of the copolymers reveal regions of amorphous and crystalline domain. Thermal studies indicate a marginally higher thermal stability for poly(aniline-co-m-amino benzoic acid) compared to poly(aniline-co-o-amino benzoic acid). (C) 2002 Elsevier Science Ltd. All rights reserved.

Synthesis of nanocomposites of Ni-Zn ferrite in aniline formaldehyde copolymer and studies on their pyrolysis products

Synthesis of nanoparticles of Ni-Zn ferrite dispersed in aniline formaldehyde copolymer using a room temperature route and the effect of heat treatment on these samples were studied using XRD, FTIR spectroscopy, Fe-57 Mossbauer spectroscopy and TEM microscopy. The results show the formation of nanosized particles of Ni-Zn ferrite in the polymer matrix at room temperature. On pyrolysis, the Ni-Zn ferrite phase persists up to 500 degreesC. However, heating of composites to 700 degreesC results in the partial reduction of the spinet ferrite leading to the formation of Ni-Fe alloy under ambient conditions and complete reduction of the alloy on heating in inert atmosphere. (C) 2003 Elsevier B.V. All rights reserved.

Fluorescence quenching of biologically active carboxamide by aniline and carbon tetrachloride in different solvents using Stern-Volmer plots

Fluorescence quenching of biologically active carboxamide namely (E)-2-(4-chlorobenzylideneamino)-N-(2-chlorophenyl)-4,5,6,7-tetrahydrobe nzo[b]thiophene-3-carboxamide [ECNCTTC] by aniline and carbon tetrachloride (CCl(4)) quenchers in different solvents using steady state method and time resolved method using only one solvent has been carried out at room temperature to understand the role of quenching mechanisms. The Stern-Volmer plot has been found to be linear for all the solvents studied. The probability of quenching per encounter p (p') was determined in all the solvents and was found to be less than unity. Further, from the studies of rate parameters and life time measurements in n-heptane and cyclohexane with aniline and carbon tetrachloride as quenchers have been shown that, the phenomenon of quenching is generally governed by the well-known Stern-Volmer (S-V) plot. The activation energy E(a) (or E(a)') of quenching was determined using the literature values of activation energy of diffusion E(d) and the experimentally determined values of p (or p'). It has been found that, the activation energy E(a) (E(a)') is greater than the activation energy for diffusion E(d) in all solvents. Hence, from the magnitudes of E(a) (or E(a)') as well as p (or p') infer that, the quenching mechanism is not solely due to the material diffusion, but there is also contribution from the activation energy. (C) 2011 Elsevier B.V. All rights reserved.

Solvent effect on the fluorescence quenching of biologically active carboxamide by aniline and carbon tetrachloride in different solvents using S-V plots

The fluorescence quenching studies of carboxamide namely (E)-N-(3-Chlorophenyl)-2-(3,4,5-trimethoxybenzylideneamino)-4,5,6,7 tetrahydrobenzob]thiophene-3-carboxamide ENCTTTC] by aniline and carbon tetrachloride in six different solvents namely toluene, cyclohexane, n-hexane, n-heptane, n-decane and n-pentane have been carried out at room temperature with a view to understand the quenching mechanisms. The Stern-Volmer (S-V) plots have been found to be nonlinear with a positive deviation for all the solvents studied. In order to interpret these results we have invoked the ground state complex formation and sphere of action static quenching models. Using these models various quenching rate parameters have been determined. The magnitudes of these parameters suggest that sphere of action static quenching model agrees well with the experimental results. Hence the positive deviation is attributed to the static and dynamic quenching. Further, with the use of Finite Sink approximation model, it was possible to check these bimolecular reactions as diffusion-limited and to estimate independently distance parameter R' and mutual diffusion coefficient D. Finally an effort has been made to correlate the values of R' and D with the values of the encounter distance R and the mutual coefficient D determined using the Edward's empirical relation and Stokes Einstein relation. (C) 2011 Elsevier B.V. All rights reserved.

Cyclopentac]thiophene oligomers based solution processable D-A copolymers and their application as FET materials

Two new solution processable, low band gap donor-acceptor (D-A) copolymers (P1 and P2) comprising a cyclopentac] thiophene (CPT) based oligomers as donors and benzoc]1,2,5] selenadiazole (BDS) and 2-dodecyl1,2,3]-benzotriazole (BTAz) as acceptors were synthesized and characterized and their field effect transistor properties were studied. The internal charge transfer interaction between the electron-donating CPT based oligothiophene and the electron-accepting BDS or BTAz unit effectively reduces the band gap in polymers to 1.3 and 1.66 eV with low lying highest occupied molecular orbital (HOMO). The absorption spectrum of P1 was found to be more red shifted than that of P2 because of incorporation of the more electron-withdrawing BDS unit. The color of neutral P1 was found to be green in both solution and film states with two major bands in the absorption spectra; however, neutral P2 revealed one dominant absorption exhibiting red color in both solution and film state which could be attributed to the less electron-withdrawing effect of the BTAz unit. The polymers were further characterized by GPC, TGA, DSC and cyclic voltammetry. P1 and P2 exhibited charge carrier mobilities as high as 9 x 10(-3) cm(2) V-1 s(-1) and 2.56 x 10(-3) cm 2 V-1 s(-1), respectively with the current on/off ratio (I-on/I-off) in the order of 10(2).

C12-Helix development in ()n sequences - spectroscopic characterization of Boc-Aib-4(R)Val]-OMe oligomers

The solution conformations of the -hybrid oligopeptides Boc-Aib-4(R)Val]n-OMe (n = 1-8) in organic solvents have been probed by NMR, IR, and CD spectroscopic methods. In the solid state, this peptide series favors C12-helical conformations, which are backbone-expanded analogues of 310 helices in -peptide sequences. NMR studies of the six- (n = 3) and 16-residue (n = 8) peptides reveal that only two NH protons attached the N-terminus residues Aib(1) and 4(R)Val(2) are solvent-exposed. Sequential NiH-Ni+1H NOEs characteristic of local helical conformations are also observed at the residues. IR studies establish that chain extension leads to a large enhancement in the intensities of the hydrogen-bonded NH stretching bands (3343-3280 cm-1), which suggest elongation of intramolecularly hydrogen-bonded structures. The development of C12-helical structures upon lengthening of the sequence is supported by the NMR and IR observations. The CD spectra of the ()n peptides reveal a negative maximum at ca. 206 nm and a positive maximum at ca. 192 nm, spectral feature that are distinct from those of 310 helices in -peptides.

Long-lived oscillatory incoherent electron dynamics in molecules: trans-polyacetylene oligomers

We identify an intriguing feature of the electron-vibrational dynamics of molecular systems via a computational examination of trans-polyacetylene oligomers. Here, via the vibronic interactions, the decay of an electron in the conduction band resonantly excites an electron in the valence band, and vice versa, leading to oscillatory exchange of electronic population between two distinct electronic states that lives for up to tens of picoseconds. The oscillatory structure is reminiscent of beating patterns between quantum states and is strongly suggestive of the presence of long-lived molecular electronic coherence. Significantly, however, a detailed analysis of the electronic coherence properties shows that the oscillatory structure arises from a purely incoherent process. These results were obtained by propagating the coupled dynamics of electronic and vibrational degrees of freedom in a mixed quantum-classical study of the Su-Schrieffer-Heeger Hamiltonian for polyacetylene. The incoherent process is shown to occur between degenerate electronic states with distinct electronic configurations that are indirectly coupled via a third auxiliary state by vibronic interactions. A discussion of how to construct electronic superposition states in molecules that are truly robust to decoherence is also presented

Influence of aniline on Daphnia magna Straus [Translation from: Trudy Saratov.Otdeleniya GosNIORKh 13 102-104, 1975]

Experiments were carried out by the method of direct effect of the tested substance on increase of biomass (1,2). Daphnia magna was cultured under laboratory conditions.The author concludes that concentrations of aniline from 5000 to 0.1 mg/1 appear acutely lethal. The disturbance of feeding, reproduction, the disorganization of the nervous system, speak of the toxicity of the substance.

Synthesis of biodegradable and electroactive multiblock polylactide and aniline pentamer copolymer for tissue engineering applications

To obtain one biodegradable and electroactive polymer as the scaffold for tissue engineering, the multiblock copolymer PLAAP was designed and synthesized with the condensation polymerization of hydroxyl-capped poly(L-lactide) (PLA) and carboxyl-capped aniline pentamer (AP). The PLAAP copolymer exhibited excellent electroactivity, solubility, and biodegradability. At the same time, as one scaffold material, PLAAP copolymer possesses certain mechanical properties with the tensile strength of 3 MPa, tensile Young 's modulus of 32 MPa, and breaking elongation rate of 95%.