A two-dimension medium band gap conjugated polymer based on 5,10-bis(alkylthien-2-yl)dithieno[3,2-d:3′,2′-d′]benzo[1,2-b:4,5-b′]dithiophene: Synthesis and photovoltaic application

A two-dimension medium band gap copolymer poly{5,10-bis(4,5-didecylthien-2-yl)dithieno[2,3-d:2′,3′-d′]benzo[1,2-b:4,5-b′]dithiophene-2,7-diyl-alt-2,5-di(3-octylthien-2-yl) thiophen-5,5′-diyl}, named as PDTBDT-T-3T, was prepared by the palladium-catalyzed Stille cross coupling reaction and characterized. The resulting polymer exhibits good solubility in common organic solvents, excellent thermal stability, and extensive light absorption from 300 nm to 650 nm with an optical band gap of 1.92 eV, the highest occupied molecular orbital (HOMO) level of ?5.03 eV and the hole mobility up to 1.92 × 10^?4 cm²·V^?1·s^?1. The power conversion efficiencies (PCEs) of 2.02%–3.19% have been achieved in the traditional PVCs for the copolymer. It should be noted that the PCEs of 4.2% for the inverted PVCs from the copolymer with PFN (poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctyl- fluorene)]) as cathode modifying interlayer, were similar with the PCEs of 4.39% for the inverted PVCs from P3HT:PC₇₁BM at the same condition. These results indicated that the copolymer could be used as potential candidate for P3HT.     

Synthesis of N-substituted imidazo[4,5-e]benzo[1,2-c;3,4-c’]difuroxans

N-Substituted imidazo[4,5-e]benzo[1,2-c;3,4-c’]difuroxans were synthesized by phase-transfer catalyzed alkylation of imidazo[4,5-e]benzo[1,2-c;3,4-c’]difuroxan salts with various alkylating agents. Acid hydrolysis of N-(ethoxycarbonylmethyl)imidazo[4,5-e]benzo-[1,2-c;3,4-c’]difuroxans gives the corresponding carboxylic acids. Structures of the synthesized compounds were confirmed by NMR spectroscopy, high resolution mass spectrometry, IR spectroscopy, and elemental anslysis.

     

Large branched alkylthienyl bridged naphtho[1,2-c:5,6-c′]bis[1,2,5]thiadiazole-containing low bandgap copolymers: Synthesis and photovoltaic application

Two donor-acceptor (D-A) type low bandgap (LBG) alternating conjugated copolymers containing larger conjugation planarity and stronger electro-withdrawing ability naphtho[1,2-c:5,6-c′]bis[1,2,5]thiadiazole (NT) unit, namely, poly[4,8-bis(5-(n-octylthio)thien-2-yl)-benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl-alt-4,9-bis(4-(2-decyltetradecyl)thien-2-yl)naphtho- [1,2-c:5,6-c′]bis[1,2,5]thiadiazole-5,5′-diyl] (PBDT-TS-DTNT-DT) and poly[4,8-bis(triiso-propylsilylethynyl)benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl-alt-4,9-bis(4-(2-decyltetradecyl)-thien-2-yl)naphtho[1,2-c:5,6-c′]bis[1,2,5]thiadiazole-5,5′-diyl] (PBDT-TIPS-DTNT-DT), were prepared by the palladium-catalyzed Stille polycondensation and characterized by gel permeation chromatography (GPC), UV-Vis absorption, thermal gravimetric analysis (TGA), cyclic voltammetry (CV) etc. PBDT-TS-DTNT-DT and PBDT-TIPS-DTNT-DT show the broader absorption and deeper highest occupied molecular orbital (HOMO) energy level approximately ?5.45 and ?5.62 eV, respectively. Bulk-heterojuction solar cells based on the resulted polymers and [6,6] phenyl-C₆₁ butyric acid methyl ester (PC₆₁BM) blends, with the device configuration of ITO/PFN/polymer:PC₆₁BM/MoO₃/Ag were prepared and investigated. The results showed the power conversion efficiency (PCE) of 2.67% for PBDT-TS-DTNT-DT/PC₆₁BM (w:w, 1:2) and 0.64% for PBDT-TIPS-DTNT-DT/PC₆₁BM (w:w, 1:1), with relatively high open-circuit voltage (V_OC) of 0.86 and 1.05 V, small short-circuit current (J_SC) of 5.41 and 0.97 mA cm^?2 and moderate fill factor (FF) of 57.8% and 62.4%, under an AM1.5 simulator (100 mWcm^?2), respectively.     

Synthesis and characterization of NLO chromophore with benzo [1,2-b:4,5-b′]dithiophene unit as π-electron bridge

A novel chromophore BDT–TCF with benzo[1,2-b:4,5-b′]dithiophene (BDT) unit as electron bridge was synthesized and characterized by UV–vis, NMR spectroscopy, and thermal analysis. It is the first time that BDT unit was introduced into NLO materials. The chromophore showed excellent solubility in most common solvents, and good thermal stability for practical applications. The second order nonlinear optical effect was measured by hyper Rayleigh scattering method. The diagonal hyperpolarizability β_zzz of BDT–TCF was 8.2 × 10^?28 and 9.3 × 10^?29 esu in THF solvent and in PMMA polymer matrices, respectively. The potential NLO response indicates that BDT unit is a promising π-electron bridge and an excellent candidate for nonlinear optical devices.     

Organic solar cells based on chlorine functionalized benzo[1,2-b:4,5-b′]difuran-benzo[1,2-c:4,5-c′]dithiophene-4,8-dione copolymer with efficiency exceeding 13%

Benzo[1,2-b:4,5-b′]dithiophene(BDT) has been widely used to construct donor-acceptor(D-A) copolymers in organic solar cells(OSCs). However, benzo[1,2-b:4,5-b′]difuran(BDF), an analogue of BDT, has received less attention than BDT. The photovoltaic performance of BDF copolymers has lagged behind that of BDT copolymers. Here, we designed and synthesized two BDF copolymers, PBF1-C and PBF1-C-2Cl. PBF1-C-2Cl, which is composed of BDF and benzo[1,2-c:4,5-c′]dithiophene-4,8-dione connected by a chlorinated thiophene π-bridge, displays a low-lying highest occupied molecular orbital energy level,which helps in yielding a high open-circuit voltage(V_(oc)) in OSCs. As a result, when blended with Y6, PBF1-C-2Cl-based devices showed a high V_(oc) of 0.83 V and a power conversion efficiency(PCE) of 13.10%. To the best of our knowledge, the PCE of 13.10% is among the highest efficiency values for OSCs based on BDF copolymers.     

化合物[2,6-bis(benzo[1,2-d:4,5-d′]diimidazole-2′-yl)pyridine] 的合成、晶体结构和光物理性质

A new tridentate benzimidazole derivative, 2,6-bis (benzo[1,2-d:4,5-d′]diimidazole-2′-yl) -pyridine (Bzdiimpy),was prepared from o-phenylenediamine in five steps with improved methods according to the literature in good yield.The crystal structure was determined by X-ray diffraction analysis. It crystallized in monoclinic, space group P21/c,with a=1.1708(4) nm, b=2.4796(9) nm, c=1.215 9(4) nm,β=114.641(7)°, Z=1, R=0.035 0, wR2=0.0890. The bzdiimp molecule displayed an almost planar structure and formed a zig-zag chain through weak interactions between imidazole-N and [SnCl6]2--Cl. Its electronic absorption and emission spectra were measured and compared with the reported analogue 2,6-bis (benz[1,2-d:4,5-d′]imidazole-2′-yl)-pyridine (Bzp).     

Synthesis of Bisindolylindeno[1,2-b]quinoxaline and Bisindolylindeno[3,4-b]pyrazine with Poly(N,N′-dibromo-N-ethylnaphthyl-2,7-disulfonamide)

Poly(N,N′-dibromo-N-ethylnaphthyl-2,7-disulfonamide) (PBNS) as novel reagent was synthesized. Bisindolylindeno[1,2-b]quinoxaline and bisindolylindeno[3,4-b]pyrazine derivatives were synthesized in a simple and efficient method from the three-component condensation reaction of indole, indane-1,2,3-trione, and diamine aromatic compounds by PBNS under solvent-free conditions at 80 °C in good to excellent yields, short reaction times, and a simple procedure for new derivatives.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications^® for the following free supplemental resource(s): Full experimental and spectral details.]     

Synthesis and photoelectric properties of an organic dye containing benzo[1,2-b：4,5-b’]dithiophene for dye-sensitized solar cells

A novel benzodithiophene-containing organic dye BDT was synthesized and characterized as a sensitizer for a nanocrystalline TiO₂-based dye-sensitized solar cell.The BDT dye shows two major electronic absorptions.The absorption of the BDT dye covers a broad visible range from 300 nm to 550 nm.The benzodithiophene unit was used as aπbridge with several advantages:（1） It facilitates the electron transfer from the donor to the acceptor;（2） A facile structural modification on the 4,8-positions in the benzodithiophene unit can be achieved;（3） Fusing benzene with two flanking thiophene units improves the thermal stability.Under simulated AM1.5G solar light（100 mW/cm²） illumination,the DSC based on BDT gives a power conversion efficiency of 1.78%.     

Synthesis and Reactivity of 2-(Furan-2-yl)benzo[1,2-d:4,3-d′]bis[1,3]thiazole

Russian Journal of Organic Chemistry - Acylation of 1,3-benzothiazol-6-amine with furan-2-carbonyl chloride in propan-2-ol gave N-(1,3-benzothiazol-6-yl)furan-2-carboxamide which was converted to...     

化合物[2,6-bis(benzo[1,2-d:4,5-d']diimidazole-2'-yl)pyridine]的合成、晶体结构和光物理性质(英文)

0IntroductionBenzimidazoleanditsderivativeshaveattractedagreatattentionintherecentyearsduenotonlytotheirbiologicalactivities[1,2],butalsostrongcoordina鄄tionabilitiesasmultidentateligandsandtheirmetalcomplexeshavingabroadscopeofproperties.Forex鄄ample,pyr…     

Synthesis of cycloocta[2,1-b:3,4-b′]diquinoline and cycloocta[2,1-b:3,4-b′]di[1,8]naphthyridine,and x-ray crystal structures of cycloocta[2,1-b:3,4-b′]diquinoline and its 2:1 complex with copper (I) perchlorate

New compounds containing a diquinoline or 1,8-dinaphthyridine nucleus fused to the molecular skeleton of cyclooctatetraene have been synthesized. An X-ray analysis of cycloocta[2,1-b:3,4-b′] diquinoline ($\text{1}$) has revealed that the molecule contains a C₂ axis. The reaction of $\text{1}$ with copper (II) perchlorate furnished a complex of formula [($\text{1}$)₂Cu]ClO₄, the coordination geometry about the copper (I) atom being that of a flattened tetrahedron.     

5-[4-amino(1,2,5)oxadiazolyl]-5H-[1,2,3]tri-azolo [4,5-c][1,2,5]oxadiazole from 4,4′-diamino-3,3′-azofurazane

4,4-Diamino-3,3-azofurazane undergoes intramolecular oxidative cyclization to give 5-[4-amino(1,2,5)oxadiazolyl]-5H-[1,2,3]triazolo[4,5-c][1,2,5]oxadiazole upon heating with Pb(OAc)₄ in chlorobenzene oro-dichlorobenzene or with thionyl chloride.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 253–254, February, 1996.     

Preparation and Determination of 4,8-Diethylbenzo-[1,2- d :4,5- d ′]bis[1,2,3]trithiole Dication [DEBBT(2+)]

Abstract

Preparation and detection of DEBBT(2+)-? S and DEBBT(2+)-? T are reported.     

Synthesis,Reactions, and Antiviral Activity of 1-(1H-Pyrazolo[3,4-b]pyridin-5-yl)ethanone and Pyrido[2′,3′:3,4]pyrazolo[5,1-c][1,2,4]triazine Derivatives

1-(3-Amino-6-methyl-4-pyridin-3-yl-1H-pyrazolo[3,4-b]pyridin-5-yl)ethanone (3) was obtained in very pure state and used as a good starting material for the present study. It diazotized to give the corresponding diazonium salt 9 and also reacted with phenyl isothiocyanate to give the corresponding thiourea derivative 4. Compound 4 was used for the preparation of thiazole derivatives 5–8 via the reaction with active halogen-containing compounds. On the other hand, compound 9 coupled with several active –CH₂- containing compounds to afford the corresponding triazine derivatives 10–17. Considering the data from IR, ¹ H NMR, mass spectra, and elemental analyses, the chemical structures of the newly synthesized heterocyclic compounds were elucidated. Cytotoxicity, anti-HSV1, and anti-HAV-MBB activity were evaluated for the newly synthesized heterocyclic compounds.     

Synthesis and structure of 2-methyl-6-oxo-7,8-dihydrospiro(benzo[h]-triazolo[3,4-b]quinazoline-7,1′-cyclopentane)

The reaction of 4-amino-3-ethoxycarbonyl-1,2-dihydrospiro(naphthalene-2,1-cyclopentane) with benzoyl isothiocyanate led to the corresponding 4-(N-benzoylthioureido) derivative, the cyclization of which gave 4-oxo-2-thioxo-1,2,3,4,5,6-hexahydrospiro(benzo[h]qquinazoline-5,1-cyclopentane). Condensation of the latter with hydrazine hydrate gave 2-hydrazino-3,4,5,6-tetrahydrospiro(benzo[h] quinazoline-5,1-cyclopentane), which formed 6-oxo-1H-7,8-dihydrospiro(benzo[h] triazolo[3,4-b] quinazoline7,1-cyclopentane) in reaction with orthoformice ester. Methylation of the product with methyl iodide led to its 2-methyl derivative.Communication 1, see ref. [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 658–662, May, 2000.     

Etudes infrarouge et NMR d'aryl-2 dihydro-1,2 (4H) thiéno[2,3-c]benzo[e]pyrannones-4

The spectroscopic properties (i.r., NMR) of 2-aryl-1,2-dihydro (4H) thiéno[2,3-c]benzo[e]pyrane-4-ones have been studied. Chemical shifts and coupling constants of dihydrothienylic protons are affected by substitutions on the aryl ring and on homocycle 2′, 8 and 9 positions to give a conformational approach of these new compounds. The crystal structure of 2-phenyl dihydrothiénocoumarine agrees the results of the spectroscopic study.     

化合物[2，6-bis(benzo[1，2-d：4，5-d′]diimidazole-2′-yl)pyridine]的合成、晶体结构和光物理性质(英)

A new tridentate benzimidazole derivative, 2,6-bis (benzo[1,2-d:4,5-d′]diimidazole-2′-yl) -pyridine (Bzdiimpy), was prepared from o-phenylenediamine in five steps with improved methods according to the literature in good yield. The crystal structure was determined by X-ray diffraction analysis. It crystallized in monoclinic, space group P2₁/c, with a=1.170 8(4) nm, b=2.479 6(9) nm, c=1.215 9(4) nm, β=114.641(7)°, Z=1, R=0.035 0, wR₂=0.089 0. The bzdiimp molecule displayed an almost planar structure and formed a zig-zag chain through weak interactions between imidazole-N and [SnCl₆]^2--Cl. Its electronic absorption and emission spectra were measured and compared with the reported analogue 2,6-bis (benz[1,2-d:4,5-d′]imidazole-2′-yl)-pyridine (Bzp). CCDC: 239203.     

Studies on Condensed Heterocyclic Compounds(Ⅲ)——Synthesis and Antibacterial Activity of 3-(4-Pyridyl)-6-Alkyl/Aromatic Heterocyclyl-s-Triazolo[3,4-b]-1, 3,4-Thiadiazoles and 1,4-Bis [6-(4-Pyridyl)-s-Triazolo [3,4-b]-1, 3,4-Thiadiazol-3-yl]-n-Butane

In recent years, fused heterocycles have been reported to possess important properties in synthesis and pharmacology. Especially, s-triazolo, 3,4-thiadiazole derivatives have been attracting much attention for chemists and pharmacologists because they show broad spectra of biological activities, such as antifungal, antibacterial, hy-