The preparation of a new thiophenic dimer partially derivatized with a bromohexylic chain is described. its polymerization under mild oxidative conditions leads to a polythiophene with a degree of functionalization Of 50% and highly soluble in organic solvents. The product has been fully characterized by FT-IR, H-1 and C-13 NMR using one and two-dimensional techniques as well as by SEC and thermal analysis. Solvatochromic effects of the new polymer have been investigated in different mixtures, underlining its self-assembling capability even in solvated states.

A thiophene-based conjugated polymer bearing a cyano group (–CN) as a side chain substituent was successfully synthesized. The polymer evidences an excellent filmability from various organic solvents as well as an enhanced photoluminescence. The polymer has been characterized optically (Fourier Transformed Infrared spectroscopy, absorption and photoluminescence) in solution and in film, while X-ray diffraction measurements (XRD) of thin films were performed to investigate its bulk morphological features. From the absorption edge of the spectrum of a thin polymer film, the optical band gap of the polymer is estimated to be 2.0 eV, which corresponds to orange emission. Furthermore, a single layer light emitting diode (LED) was fabricated. The device produced bright stable electroluminescence at room temperature. All of the results indicate that this polymer is a promising emissive material for application in polymeric LEDs.

Copolymerizations at various feed ratios between azo-dye-substituted thiophenes and 3-hexylthiophene under FeCl3-based oxidative conditions have been conducted. It is shown that when the molecular structure of the dye is properly designed, completely soluble copolymers, with molecular weigths ranging around 10(4) as M-n and dye-substituted monomer content up to 50% in a molar ratio, may be prepared, as well as a completely soluble homopolymer. In addition, the so-obtained polymers evidenced excellent filmability from a variety of solvents. The dye-substituted monomer content of the soluble copolymers has been assessed by H-1 NMR analysis via a convenient choice of the reference signals. In the completely soluble copolymers the dye-substituted monomer content is well correlated to the feed within a range between 0 and 75% of dye-substituted unit in the feed, which corresponds to a 0-50% range in the copolymer composition, still conserving satisfactory molecular weights. Following these observations and analyzing the characteristics of the polymers, a lower reactivity of the dye-functionalized unit toward 3-hexylthiophene was evidenced in the used reaction conditions, and some hypotheses on this finding are presented.

The synthesis and chemical polymerization of a thiophene disubstituted with an alkylic and an ω-bromine functionalized oligomethylenic chain is described. The obtained polymer, namely the poly[3-hexyl-4-(6-bromohexyl)thiophene], is completely soluble in common organic solvents and its structural, thermal and chemical–physical properties are compared with those of a ‘conventional’ bromohexyl 3-substituted polythiophene. The new polymer may be considered as a key-intermediate for the synthesis of multifunctional soluble polythiophenes since its self-plastifying feature may permit the insertion on the polymeric side-chains, by simple post-polymerization functionalization reactions, of sterically demanding or strongly interacting functional groups, without final solubility being compromised.

The preparation of a regioregular trimethylsilanyloxydecyl 3-substituted polythiophene and its conversion to the corresponding hydroxydecyl polymer, which is soluble in common organic solvents, is described both in solution and in film. The chromic behaviour of the hydroxy functionalized polymer was investigated by UV–vis spectroscopy in different solvent/non-solvent mixtures and in the solid state by exposing the polymer adsorbed on hydroxylic matrices to methanol vapours.

For the purpose of preparing materials for nonlinear optics applications, a 3-ethylthiophene bearing an NLO-active chromophoric group as a substituent at the end of the ethylic chain was copolymerized with 3-hexylthiophene. Different FeCl3-based oxidative polymerization conditions in solvents such as CH3NO2 and CCl4 and their effects on the copolymers characteristics and solubility in CHCl3 (i.e., the copolymer's soluble fraction) were examined. This work allowed to achieve a satisfactory chloroform-soluble fraction of the copolymer, still containing a notable amount of NLO-active group, and to tune to some extent the main characteristics of the copolymer; moreover, the behavior of the monomers-solvent-oxidant system was investigated.

Functionalized second-order nonlinear optical (NLO) thiophene copolymers were synthesized. Two elegant syntheses based on the post-functionalization of polymeric precursors obtained by oxidative polymerization were developed, leading to copolymers that proved to be fully soluble in common organic solvents. The new materials were characterized by NMR, FT-IR, and UV vis spectroscopies, gel permeation chromatography (GPC), and thermogravimetric analysis (TGA). Moreover, the NLO activity of the new materials, as determined by corona poling alignment and second harmonic generation (SHG) measurements, showed a good agreement between the second-order NLO coefficient and the chromophore concentration.

A method of synthesis leading to poly(3-alkylthiophene)s with two different functional groups in the side chain, one of which is an NLO-active chromophore, has been developed. This method, based on the post-functionalization of a reactive homopolymeric precursor, permits to prepare different polyfunctional polymers that are fully soluble in the most commonly used organic solvents. The procedure is very easy to perform, cost-effective, highly versatile and reproducible.

The chromic behaviour of a soluble ω-hydroxydecyl 3-substituted polythiophene has been investigated by UV–VIS spectroscopy in different solvent/non-solvent mixtures over a wide range of low temperatures. Some interesting new effects have been observed that is the first case of a reversal of the solvatochromic transformation in substituted polythiopenes and a concentration effect in dilute pure solvent solutions. A molecular approach based on solvent–polymer interactions has been adopted to study the conformational chromic transformation of the polymer.

New soluble functionalized 3-alkylthiophene copolymers have been prepared by a chemical oxidative method with FeCl3. The starting comonomers were 3-hexylthiophene and 3-alkylthiophenes with an azobenzene chromophore grafted to the side chains. Characterizations of the copolymers have been reported.

A series of thiophenic monomers functionalized with different chromophoric groups have been optically characterized in view of preparation of polymeric films for second-order nonlinear optics and electrooptics. In order to investigate the optical behaviour inside a solid host matrix, the molecules have been physically dispersed in poly(methylmethacrylate) (PMMA) films and poled through high-temperature corona-poling for characterization through in situ second harmonic generation and ex situ angle-resolved spectroscopy. The values of dipole moment μ and optical hyperpolarizability β have been estimated inside the host matrix and related to the molecular structure. For one of the chromophores the long-term reorientation dynamics has been monitored in order to investigate the stability and the interaction with the polymeric environment.

The solvatochromic behavior of chloroform solutions of poly(3-decyl-2,5-thienylene), poly[3-(10-hydroxydecyl)-2,5-thienylene] and their copolymers was studied by the addition of the non-solvent methanol. A reversed chromic transformation was found associated with the content of the hydroxyalkyl substituent. This anomalous effect was investigated using a number of non-solvents, in particular aliphatic alcohols from methanol up to decanol. In the case of a chloroform/methanol mixture, which gives the maximum anomalous effect, the effect produced by temperature variation was also examined. An explanation based on a molecular approach was attempted.

An alternating methoxyhexylthiophene–thiophene copolymer was synthesized from 3-(6-methoxyhexyl)-2,2′-bithiophene and studied chiefly by means of optical absorption and nuclear magnetic resonance spectroscopy. The results were compared with those of the previously obtained poly[3-(6-methoxyhexyl)-2,5-thienylene]. The differences in the UV-Vis spectra of the two polymers in pure solvents, solvent/non-solvent mixtures and in films are discussed on the basis of the microstructure and the steric hindrance along the backbone. NMR spectroscopy revealed copolymer configuration to be regiorandom with a slight prevalence of head-to-head and tail-to-tail junctions.

The preparation of a hexanoyloxydecyl 3-substituted polythiophene and its conversion to the corresponding hydroxydecyl polymer, soluble in common organic solvents, is described. Solvatochromic and thermochromic effects of the two polymers were investigated by UV-vis spectroscopy in pure solvent and in solvent/nonsolvent solutions. A very different response was found depending on the type of functional group. The carboxylate polymer requires synergy of both nonsolvent and low temperature for a strong chromic effect comparable to that of the hydroxy polymer to be observed. A possible explanation of this behavior is discussed. (C) 1998 John Wiley & Sons, Ltd.

A direct sulfur insertion in N,N′-diphenyl-p-phenylenediamine was carried out to prepare the model oligomeric compound triphenodithiazine (TPDT). During the investigation of the thionation reaction variables some addition compounds, with compositions (TPDT) x S y , were isolated. Iodine doping enhanced the conductivity of the pristine compounds by 8 orders of magnitude, up to 10 −3 S/cm. Differences in iodine content and conductivity were found between TPDT and its sulfur adducts. Finally, the infrared spectrum of doped TPDT was examined.

ChemInformVolume 18, Issue 35 Heterocyclic Compounds ChemInform Abstract: A New Simple Synthesis of Electroconducting Triphenodithiazine. C. DELLA CASA, C. DELLA CASA Inst. Chim. Intermedi, Univ., 40136 Bologna, ItalySearch for more papers by this authorP. COSTA BIZZARRI, P. COSTA BIZZARRI Inst. Chim. Intermedi, Univ., 40136 Bologna, ItalySearch for more papers by this authorF. ANDREANI, F. ANDREANI Inst. Chim. Intermedi, Univ., 40136 Bologna, ItalySearch for more papers by this author C. DELLA CASA, C. DELLA CASA Inst. Chim. Intermedi, Univ., 40136 Bologna, ItalySearch for more papers by this authorP. COSTA BIZZARRI, P. COSTA BIZZARRI Inst. Chim. Intermedi, Univ., 40136 Bologna, ItalySearch for more papers by this authorF. ANDREANI, F. ANDREANI Inst. Chim. Intermedi, Univ., 40136 Bologna, ItalySearch for more papers by this author First published: September 1, 1987 https://doi.org/10.1002/chin.198735243Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume18, Issue35September 1, 1987 RelatedInformation

Preparation et complexation de ce polymere avec l'acide chlorosulfonique qui permet d'augmenter la conductivite de 11 ordres de grandeur

The stereoselectivity of the title reactions due to a hindering amino group in α-asymmetric aminoketones (1 and 2) and to an asymmetric center far away from the reaction center in β-(methylpiperidino)-ketones (11–14) has been studied. The aminoalcohols obtained (3–8 and 15–22) have been separated in most cases and the relative configurations attributed by NMR. Based on diastereomeric ratios, a N-coordinated cyclic transition state has been proposed and is, effective at least for the Grignard reactions on the β-aminoketone system.

The stereoselectivity of the title reactions due to a hindering amino group in α-asymmetric aminoketones (1 and 2) and to an asymmetric center far away from the reaction center in β-(methylpiperidino)-ketones (11–14) has been studied. The aminoalcohols obtained (3–8 and 15–22) have been separated in most cases and the relative configurations attributed by NMR. Based on diastereomeric ratios, a N-coordinated cyclic transition state has been proposed and is, effective at least for the Grignard reactions on the β-aminoketone system.