Synthesis and properties of polysulfonamides containing thiophene links

In order to study the synthesis and properties of polysulfonamides containing thiophene links, 2,2-bis(5-chlorosulfonyl-2-thienyl)propane [BCTP], 2,2-bis(5-chlorosulfonyl-2-thienyl)butane [BCTB], 1,1-bis(5-chlorosulfonyl-2-thienyl)cyclohexane [BCTC], and 2,4-dichlorosulfonyl thiophene [DCST] were prepared and interfacial polycondensations with various aliphatic diamines were carried out. The resulting polymers had inherent viscosities in the range of 0.13–0.41 dL/g and showed high extent of moisture absorptions. Most of the polysulfonamides were soluble in electron-donating solvents such as pyridine, DMF, DMSO, NMP, etc. These polysulfonamides exhibited relatively good thermal stabilities. The TGA data revealed 5% weight losses at 275–405°C and residual weights at 500°C were 13–40% under nitrogen. It was also found that dithienyldisulfonyl chlorides produced more thermally stable polymers than DCST, which were comparable to common polysulfonamides from aromatic disulfonyl chlorides.     

Synthesis and properties of vinyl‐terminated and silicon‐containing polysulfones and polyketones

4‐Fluorophenylsulfonylphenyl‐terminated polysulfone and 4‐fluorobenzoylphenyl ketone were prepared with bisphenol A and an excess of bis‐(4‐fluorophenyl)sulfone or 4,4′‐difluorobenzophenone, respectively, at 160 °C using potassium carbonate in N,N‐dimethylacetamide. The resulting polymers were reacted with 4‐hydroxystyrene to synthesize vinyl‐terminated polysulfones and ketones. The silicon‐containing polysulfones and ketones were prepared from the vinyl‐terminated polymer precursor and various H‐functional silanes or siloxanes. The synthesis of silicon‐containing polymers was achieved by hydrosilation with a rhodium catalyst. It was shown that the hydrosilation reaction proceeds with 55:45 chemoselectivity. The resulting polymers were investigated by ¹H NMR spectroscopy, DSC, and thermogravimetric analysis. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2937–2942, 2001     

Synthesis, characterization and photovoltaic properties of thiophene copolymers containing conjugated side-chain

Five side-chain conjugated polythiophene derivatives, P1-P5, were synthesized by Stille coupling reaction. The effects of side-chain structures, bearing CC double bond, CC triple bond as well as different number of methoxy substituents on the benzene ring of the side-chains, on the optical, electrochemical, and photovoltaic properties of the polymers were investigated. From P1 to P3, the effect of CC triple bond and CC double bond was compared. The results indicate that the content of the thiophene units with the CC triple bond in their conjugated side-chains not only influences the absorption shape and intensity, but also influences the energy bandgap and the photovoltaic properties of the polymers. From P3 to P5, the effect of methoxy substituents on the benzene ring of the conjugated side-chains was compared. On increasing the number of the methoxy groups on the benzene ring of the conjugated side chains, the visible π-π^∗ absorption of the conjugated polymer backbone become stronger both in solution and in film. Electron-donating ability of the methoxy groups decreased the bandgap of the polymers. The best polymer solar cell based on P5 with a structure of ITO/PEDOT:PSS/Polymer:PCBM (1:1 wt/wt)/Mg/Al showed a power conversion efficiency of 1.45% under the illumination of AM1.5, 80 mW/cm².     

Synthesis, characterization and antitumor properties of titanocene derivatives with thiophene containing ligands

The titanocene complexes [TiCp₂(Cl)R] (1), [TiCp₂(Cl)SR] (2), [TiCp₂(SR)₂] (3) with R = benzothienyl (BT) A and dibenzothienyl (DBT) B, were synthesized and the molecular structures of [TiCp₂(Cl)DBT] (1B) and [TiCp₂(Cl)SDBT] (2B) confirmed by single crystal X-ray diffraction studies. The dibenzothiophene rings are planar and for 1B in the plane of the titanium and chloro ligand. The chloro ligand is in a trans position to the sulfur atom with respect to the titanium-carbon bond. The complexes were studied for their electronic and structural features and preliminary tests were conducted for their tumor inhibiting properties against HeLa and COLO 320M tumor cell lines. These antitumor activities were compared against those observed for titanocene dichloride (S-01) under similar conditions and the highest antitumor activity was recorded for 2B.     

Synthesis of macrocyclic compounds containing thiophene and thiazole nuclei

Macrocyclic ketones that contain a thiophene nucleus and have 14 or more carbon atoms in the ring can form systems with a condensed thiazole ring, in high yield.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 841–844, June, 1986.     

Synthesis,processing, and third-order nonlinear optical properties of benzobisthiazole polymers containing thiophene moieties

Benzobisthiazole polymers containing mono-, bi-, and terthiophene moieties were synthesized through polycondensation in polyphosphoric acid of 2,5-diamino-1,4-benzenedithiol dihydrochloride with thiophene-2,5-dicarboxylic acid, 2,2′-bithiophene-5,5′-dicarboxylic acid, and 2,2′:5′,2″-terthlophene-5,5″-dicarboxylic acid, or their corresponding diacid chlorides, respectively. Intrinsic viscosities of up to 8.1 dL/g (methanesulfonic acid, 30°C) were recorded. Polymer structures were verified by elemental analysis and spectroscopic comparison of the polymers with appropriate model compounds. Onset of breakdown under thermogravimetric analysis in air occurred in the 460–590°C range with the benzobisthiazole polymers containing a monothiophene linkage being the most stable. Films suitable for third-order optical susceptibility measurements could be prepared by extrusion techniques from the benzobisthiazole polymer containing a monothiophene linkage. Degenerate four wave mixing measurements on this film yielded a third order optical susceptibility χ⁽³⁾ of approximately 4.5 × 10^?10 esu. © 1993 John Wiley & Sons, Inc.     

Structure and properties of new polyketones

New aromatic polyketones were obtained by reaction of terephthalolyl chloride with phenanthrene, naphthalene, 2-methylnaphthalene or 2,3-dimethylnaphthalene in the presence of anhydrous AlCl₃ in various solvents. The influence of the structure of the aromatic hydrocarbon on the thermal stability of the polymer was examined.     

Synthesis of novel azonia Helicenes containing terminal thiophene rings

The Knoevenagel condensation of the 9‐methyl derivatives of thieno[3,2‐a]‐ and thieno[2,3‐a]‐quinolizinium salts ( 2b and 3b ) with appropriate arylaldehydes yielded 9‐(arylvinyl)thieno[3,2‐a]‐ and 9‐(arylvinyl)thieno[2,3‐a]quinolizinium salts ( 4a‐c and 5a‐c ), respectively, which underwent photocyclization to give a series of novel hetero[5]helicenes ( 6a,b and 7a‐d ) containing quinolizinium and thiophene rings.     

Synthesis and photovoltaic properties of organic sensitizers containing electron-deficient and electron-rich fused thiophene for dye-sensitized solar cells

Diverse fused thiophenes with electron-rich and electron-deficient blocks have been synthesized and employed as the π-conjugated spacers of organic dyes for the dye-sensitized solar cells (DSSCs). The effects of these fused thiophenes were investigated by their absorption spectra, electrochemical and photovoltaic properties. For a typical device a maximum power conversion efficiency of 6.11% was obtained under simulated AM 1.5 irradiation (100 mW cm^?2): a short-circuit current (J_SC) of 14.47 mA cm^?2, an open-circuit voltage (V_OC) of 670 mV, and a fill factor (FF) of 0.63.     

Synthesis and second-order nonlinear optical properties of new chromophores containing benzimidazole, thiophene, and pyrrole heterocycles

A new series of thermally stable benzimidazole-based nonlinear optical (NLO) chromophores 4 and 5 have been developed. These chromophores possess a thienylpyrrolyl π-conjugated system attached to functionalized benzimidazole heterocycles. This feature leads to robust chromophores with excellent solvatochromic properties, high thermal stabilities and good molecular optical nonlinearities.     

Synthesis and nonlinear optical properties of polyacetylenes containing oxadiazole and thiophene pendant groups with high thermal stability

A series of random copolymers poly(3‐ethynylthiophene)‐copoly(2‐(4‐decyloxyphenyl)‐5‐(4‐ethynylphenyl)‐1,3,4‐oxadiazole) with different oxadiazole content ( P2 – P4 ) and homopolymer poly(3‐ethynylthiophene) ( P1 ) as well as poly(2‐(4‐decyloxyphenyl)‐5‐(4‐ethynylphenyl)‐1,3,4‐oxadiazole) ( P5 ) were prepared. The copolymers ( P2 – P4 ) are completely soluble in common organic solvents. The structures and properties of all polymers were characterized and evaluated by FTIR, ¹H NMR, ¹³C NMR, TGA, UV, PL, GPC, and nonlinear optical (NLO) analyses. The incorporation of diaryl‐oxadiazole into polyacetylene‐containing thiophene significantly endows copolymers with higher thermal stability, which may origin from the synergetic effect of the “jacket effect” of diaryl‐oxadiazole units and the effect of retarding or eliminating a few 6π‐electrocycliaztion proceeds of oxadiazole‐containing polyacetylene due to the hindrance of thiophene units. When the copolymer ( P3 ) posses more regular alternating thiophene pendants and oxadiazole pendants arrangement along the polymer backbone, it shows good thermal stability (T_d up to 388 °C) and larger third‐order nonlinear optical susceptibility (χ(3) up to 11.0 × 10^?11 esu). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis and psychotropic properties of azomethine derivatives of thiophene

A series of azomethine derivatives was obtained by condensation of 2-thiophenaldehyde and 5-substituted (alkyl, bromine, tert-butyl, trimethylsilyl)-2-thiophenaldehydes withsemicarbazide, thiosemicarbazide, aminohydantoin, and 2-semicarbazide acetic acid. Their psychotropic activity was investigated. It was found that incorporation of a ten-butyl group in position 5 of the thiophene ring potentiates the toxicity of the compound. 5-Trimethylsilyl-and 5-ten-butyl-2-thiophenaldehyde thiosemicarbazones exhibit elevated neurotropic activity. These compounds cause the stimulating effect of phenamine to appear, increasing the motor activity of animals by two times and prolonging the effect of hexenal-induced sleep. Substitution of thiosemicarbazone by semicarbazone decreases the activity except for hexenal sleep, where the 5-tert-butyl-2-thiophenaldehyde semicarbazone was 1.5 times more active than the thiosemicarbazone.Latvian Institute of Organic Synthesis, Riga, LV-1006. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 629-632, May, 1995. Original article submitted May 12, 1995.     

Synthesis, structures, and properties of disubstituted heteroacenes on one side containing both pyrrole and thiophene rings

A new series of ladder-type heteroacenes containing both pyrrole and furan rings, 5,6-disubstituted diindolo[3,2-b:4,5-b']thiophenes (DITs), were effectively synthesized from N-functionalized 3,3'-dibromo-2,2'-biindoles undergoing intramolecular cyclization with bis(phenylsulfonyl) sulfide and organolithium. Single-crystal X-ray results demonstrate that 5,6-dipropyldiindolo[3,2-b:4,5-b']thiophene (4b) forms a herringbone-type of packing motif and 5,6-di(p-tolyl)diindolo[3,2-b:4,5-b']thiophene (4d) forms a parallel packing motif. Both of them have S-S contacts, enhancing the electronic transport between molecules. Their photophysical properties suggest that the skeleton of diindolo[3,2- b:4,5-b']thiophene is more favorable to aggregate in solid than that of indolo[3,2-b]carbazole. The large band gaps and low-lying HOMO energy levels could result in much better stability.     

Synthesis and properties of polyfluorene copolymers bearing thiophene and porphyrin

To search for more wider absorption and higher charge carriers mobilities materials of polymer solar cell, a series of soluble alternating polyfluorene copolymers were synthesized by palladium-catalyzed Suzuki coupling reaction. Their structures were determined by 1H NMR, IR and UV-vis. And their UV-vis absorption spectra indicated that they had strong absorption over 600 nm spectral range and nearly cover 400-700 nm visible region. The band gaps of copolymers calculated according to cyclic voltammetry （CV） were between 1.96 and 2.03 eV. Polymer：TiO2 bulk-heterojunction films were made from mixtures of polymer and titanium isopropoxide, a precursor for TiO2, via hydrolysis in air overnight. The photoluminescence at 380-800 nm of the blend film of PT-TPP20 （5 mg/mL）：Ti（OC3H7）4 （80 μL/mL） （20% volume fraction） was significantly quenched in the 50% Ti（OC3H7）4 blend film, indicating that rapid and efficient separation of photoinduced electron-hole pairs.     

Synthesis,characterization and biological studies of ferrocenyl complexes containing thiophene moiety

A new ferrocenyl ligand was prepared from the condensation of 1,1′‐diacetylferrocene dihydrazone with 2‐thiophenealdehyde. The ligand, 1,1′‐bis[(2‐thienylmethylidene)hydrazono‐1‐ethyl]ferrocene, forms 1:1 complexes with cobalt(II), nickel(II), copper(II) and zinc(II) in good yield. Characterization of the ligand and complexes was carried out using IR, ¹H NMR, electronic absorption and elemental analysis. Biological activity of the ligand and its complexes was assessed against Bacillus subtilis (+ve), Staphylococcus aureus (+ve), Candida albicans (yeast), Esherichia coli (?ve), Salmonella typhi (?ve), Aspergillus niger (fungi), and Fusarium solani (fungi). The biological results indicated that the complexes prepared are more active than the ligand. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis, characterization and biological activity of polyketones

Polyketone resins have been prepared by the Friedel-Crafts polymerization of dithiophenylidenecyclopentanone (Ⅰ), dithiophenylidenecyclohexanone (Ⅱ) and dithiophenylideneacetone (Ⅲ) with adipoyl, sebacoyl and terephthaloyl dichlorides using boron trifluoride as catalyst and carbon disulphide as solvent. Polymers were characterized with IR, 1 H-NMR, and the results showed the presence of carbonyl of ketonic groups in the main chain. The polyketones have inherent viscosities of 0.40-0.70 dL/g. All the polymers are semicrystalline and most of them are partially soluble in most common organic solvents but freely soluble in aprotic solvents. The temperatures of 50% weight loss are as high as 185℃ to 280℃ in air, indicating that these aromatic polyketones have excellent thermal stability. All the polyketones were tested for their antimicrobial activity against bacteria and fungi.