以2,2,5,5-四氟-2,5-二氢呋喃桥连的1,2-二噻吩乙烯类光致变色分子的合成

设计并合成了新型的以2,2,5,5-四氟-2,5-二氢呋喃桥连的1,2-二噻吩乙烯类光致变色分子1,从廉价易得的六氯丁二烯出发,经醇解、氯化、关环和氟化反应合成了关键中间体全氟2,5-二氢呋喃(2),并通过与化合物3'-溴-[2,2':5',2']三噻吩(3)的偶合反应得到含氟光致变色分子1.     

小分子优先结晶构筑聚合物/非富勒烯共混体系互穿网络结构

非富勒烯小分子受体(SMAs)有序聚集决定聚合物/非富勒烯共混体系光伏电池的双分子复合几率。 然而,由于非对称相分离聚合物趋于优先形成网络,抑制小分子受体分子结晶。 在聚[(2,6-(4,8-二(5-(2-乙基己基噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩))-alt-(5,5-(1',3'-二-2-噻吩基-5',7'-二(2-乙基己基)苯并[1',2'-c:4',5'-c']二噻吩-4,8-二酮))](PBDB-T)/9-二(2-亚甲基(3-(1,1-二氰基亚甲基)-6,7-二氟-茚酮))-5,5,11,11-四(4-己基苯基)-二噻吩并[2,3-d:2',3'-d']-s-引达省[1,2-b:5,6-b']二噻吩(IT-4F)共混体系,四氢呋喃蒸汽处理可提高IT-4F结晶性,150 ℃热退火可提高PBDB-T的结晶性。 因此,依次利用蒸汽退火和热退火处理薄膜,诱导小分子先结晶、聚合物后结晶,从而降低PBDB-T对小分子扩散的限制,构建高结晶互穿网络结构。 形貌优化后降低了双分子复合,器件光电转换效率从5.95%提高至7.18%。     

高性能简单结构聚(噻吩-喹喔啉)类给体光伏材料

<正>近年来,聚合物太阳能电池(PSCs)以其重量轻、价格低廉、可通过印刷方式制备大面积柔性器件等潜在优势,得到了学术界和工业界的广泛关注,也是世界各国在新能源部署上的重要研究方向之一.窄带非富勒烯受体(如2,2’-[[6,6,12,12-四(4-己基苯基)-6,12-二氢二硫代[2,3-d:2’,3’-d’]-s-吲哚诺[1,2-b:5,6-b’]二噻吩-2,8-二基]双[亚甲基(3-氧代-1H-茚-2,1(3H)-二亚甲基)]]双[丙胺](ITIC)、2,2’-((2Z,2’Z)-((4,4,9,9-四(对己基苯)-4,9-二氢-S-引达省并二噻吩-2,7-二基)双(甲基亚基))-双-(3-氧代-2,3-二氢-1H-茚-2,1-二亚甲基))二丙二腈(IDIC))对于推动聚合物太阳能电池的发展起着至关重要的作用.     

以三聚茚为核的星型电子受体材料的合成、 表征与光伏性能

以高度平面共轭的烷基取代三聚茚为中心核, 以噻吩基团桥联, 在末端连接氰基茚酮作为拉电子基团, 设计合成了一类星型受体分子2,2',2″-{[(5,5,10,10,15,15-己基-10,15-二氢-5H-二茚[1,2-a：1',2'-c]芴-2,7,12-三基)三(噻吩-5,2-二基)]三(亚甲基)}三(3-氧杂-2,3-二氢-1H-茚-2,1-二叉)三丙二腈(NFT-C6)和2,2',2″-{[(5,5,10,10,15,15-癸基-10,15-二氢-5H-二茚[1,2-a：1',2'-c]芴-2,7,12-三基)三(噻吩-5,2-二基)]三(亚甲基)}三(3-氧杂-2,3-二氢-1H-茚-2,1-二叉)三丙二腈(NFT-C10). NFT-C6和NFT-C10的最高占据轨道(HOMO)和最低未占轨道(LUMO)分别位于-5.66和-3.75 eV. 其薄膜在400~700 nm范围内具有较大的吸收强度, 最大吸收峰分别位于606和586 nm. 以聚[(2,6-{4,8-二[5-(2-乙基己基)噻吩-2-基]-苯并[1,2-b：4,5-b']二噻吩})-{5,5-(1',3'-二-2-噻吩基-5',7'-二(2-乙基己基)苯并[1',2'-c：4',5'-c']二噻吩-4,8-二酮)}](PBDB-T)为给体材料, 以NFT-C6或NFT-C10为受体材料制备了太阳能电池器件, 器件在300~700 nm之间具有较宽的响应光谱, 其光电转换效率(PCE)分别达到1.09%和5.23%. 原子力显微镜(AFM)结果表明, PBDB-T和NFT-C10共混制备的光伏器件活性层具有合适的相分离尺寸, 有利于激子的有效解离, 而PBDB-T: NFT-C6器件的活性层相分离尺寸过大, 增加了激子复合的几率, 使器件的短路电流、 填充因子和PCE降低. 研究结果表明, 基于三聚茚的星型光伏材料具有一定的应用前景.     

两种非对称芳基二噻吩并[2,3-b:3',2'-d]噻吩的合成与光谱特性

合成了两种非对称芳基取代的并三噻吩化合物.以2-溴-5-三甲基硅-二噻吩并[2,3-b:3',2'-d]噻吩为原料,经脱除四甲基硅烷(TMS)和Suzuki偶联两步反应制备了2-噻吩基二噻吩并[2,3-b:3',2'-d]噻吩,总产率为67.4%;以2-苯基二噻吩并[2,3-b:3',2'-d]噻吩为原料,经N-溴代琥...     

含噻吩和吡啶基的插烯式四硫富瓦烯衍生物的合成、结构和电化学性质

在亚磷酸三乙酯催化作用下,2,3-二(2-吡啶硫基)-1,3-二硫环戊烯-2-硫酮(1)分别与2-噻吩甲醛(2a)和3-噻吩甲醛(2b)发生成烯偶联反应,生成二硫富瓦烯化合物[2-(2-噻吩)亚基-1,3-二硫环戊烯-4,5-二硫基]双邻吡啶(3a)和[2-(3-噻吩)亚基-1,3-二硫环戊烯-4,5-二硫基]双邻吡啶(3b);含噻吩和吡啶基的二硫富瓦烯化合物3a和3b分别经过单质碘诱导氧化偶联反应和硫代亚硫酸钠还原反应,得到含噻吩和吡啶基的插烯式四硫富瓦烯化合物1,2-双(4,5-二邻吡啶硫代-1,3-二硫环戊烯-2-亚基)-1,2-双(2-噻吩基)乙烷(4a)和1,2-双(4,5-二邻吡啶硫代-1,3-二硫环戊烯-2-亚基)-1,2-双(3-噻吩基)乙烷(4b).利用核磁共振波谱(NMR)、傅里叶变换红外光谱(FTIR)和质谱(MS)方法对插烯式四硫富瓦烯衍生物(4a和4b)分别进行了表征,同时采用X射线单晶衍射法分析确证了化合物3a,3b,4a和4b的晶体结构.循环伏安法研究结果表明,化合物4a和4b呈现准可逆的两电子转移行为.结合量子化学理论计算,探讨了噻吩基的位置差异对化合物4a和4b电化学电位的影响.     

3-疏基香豆素及其衍生物的研究

研究了3-疏基香豆素(8)、3,3'-二硫代双香豆素的合成及8与一系列Michael受体的反应.按受体结构不同,除都能发生分子间的加成反应外,有些还可进一步发生第二次分子内的加成反应,关环后得到一系列四氢噻吩并[2,3-C][1]苯并吡喃-4(H)-酮的衍生物.对这些化合物的立体化学及结构进行了鉴定.8分别和烯丙基溴、肉桂基溴缩合,前者在N,N-二甲苯胺内发生正常的Claisen重排,得到1,2-二氢-2-甲基噻吩并[2,3-C][1]苯并吡喃-4-(H)-酮及1,2,3,5-四氢硫代吡喃并[2,3-C][1]苯并吡喃-5-酮,但后者的反应产物是3-(ρ-N,N-二甲氨基)苄硫基香豆素.     

杂环酮腙与类似物的合成及其对结核杆菌的抑制活性

22个新的杂环酮腙及其类似物被合成,其对结核分枝杆菌菌株H37Rv的抑菌活性被测定.这些化合物都显示出抑菌活性.其中,化合物(1E,4E)-1,5-二(5'-溴-2'-噻吩基)-1,4-戊二烯-3-酮-(1',4',5',6'-四氢嘧啶基)腙(1d)的MIC90为2μg/m L,显示出最高的抑菌活性;同时该化合物对单耐异烟肼菌株242、耐多药菌株2312和广泛耐药菌株1220的MIC90值分别为0.25,1.0和0.5μg/m L,也表现出很好的抑菌作用.     

噻吩-咔唑-苯衍生物的设计、合成及电致变色性质

以苯和二联苯单元为核,分别在其1,4位和4,4'(对位)引入噻吩-咔唑单元,设计合成了9,9'-(1,4-亚苯基)双[3,6-双(2-噻吩)]-9-氢-咔唑(BTCPh)和9,9'-[1,1'-联苯基]-4,4'-二取代基双[3,6-双(2-噻吩)]-9-氢-咔唑(BTCBPh)2种化合物;再通过电化学聚合得到相应的交联结构聚合物,分别为聚9,9'-(1,4-亚苯基)双[3,6-双(2-噻吩)]-9-氢-咔唑(p BTCPh)和聚9,9'-[1,1'-联苯基]-4,4'-二取代基双[3,6-双(2-噻吩)]-9-氢-咔唑(p BTCBPh)薄膜.利用循环伏安法(CV)、多电位阶跃、紫外-可见-近红外(UV-Vis-NIR)吸收光谱和扫描电子显微镜(SEM)等手段对其进行了表征与电化学性能测试.结果表明,2种聚合物均表现出良好的电化学性质、相似的颜色变化、较高的光学对比度及电化学循环稳定性等优异的电致变色性质.p BTCPh聚合物薄膜比p BTCBPh表现出更快的响应速度,这可能是由于前者具有更加均匀规整的堆积结构,有利于变色过程中的离子嵌入与脱出所致.     

苯-噻吩低聚物电子结构及载流子传输性质的理论研究

采用密度泛函理论(DFT)的B3LYP/6-31G(d)方法对以低聚噻吩为端基、 苯并二噻吩(TPT)和并三噻吩(TTT)为共轭桥、 炔键为连接臂的20个模型化合物进行了计算研究. 在优化中性与离子态几何构型基础上, 获得了前线轨道能级、 电离能(IPs)、 电子亲和势(EAs)、 空穴/电子重组能(λ_h/λ_e)、 载流子迁移率(μ_h/μ_e)及吸收光谱等信息. 结果表明, 炔键的引入及端基低聚噻吩的增加对LUMO能级的调控作用较为显著, 而共轭桥的类型对HOMO能级影响较大; 合理选择端基、 共轭桥和连接臂等结构单元可对该类材料吸光波段及强度进行有效调节. 一维电荷传输模型结果表明, 所设计的化合物均是潜在的双极性有机半导体材料, 其中2,7-二([2,2':5',2'-三噻吩]-5-基)苯并[1,2-b:6,5-b']二噻吩(A3)和2,7-二(二噻吩并噻吩-2-基乙炔基)苯并[1,2-b:6,5-b']二噻吩(a-3)具有较高的电子迁移率, 值得进一步的实验探索研究.     

New Heteroaromatic Complexing Agents and Luminescence of Their Europium(III) and Terbium(III) Chelates

Twelve heteroaromatic complexing agents 9a–I were synthesized with the purpose to develop suitable labels for time-resolved luminescence-based bioaffinity assays. The relative luminescence yields, excitation maxima, and emission decay constants of their europium(III) and terbium(III) chelates were determined. According to these results, 2,2′,2″,2?-[(2,2′-bipyridine-6,6′-diyl)bis(methylenenitrilo)]tetrakis (acetic acid) ( 9e ) and 2,2′,2″,2?-[(2,2′:6′,2″-terpyridine-6,6″-diyl)bis(methylenenitrilo)] tetrakis(acetic acid) ( 91 ) are the most promising agents.     

The water-soluble indolium-based fluorescence probes for detection of the extreme acidity or extreme alkalinity

In this work, 3,3′-(((1E,1′E)-(H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diyl)bis(ethene-2,1-diyl))bis(1,1-dimethyl-1H-benzo[e]indole-3-ium-2,3-diyl))bis(propane-1-sulfonate) (1), 3,3’-(((1E,1′E)-(6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diyl)bis(ethene-2,1-diyl))bis(3,3-dimethyl-3H-indole-1-ium-2,1-diyl))bis(propane-1-sulfonate) (2), 2,2’-((1E,1′E)-(6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diyl)bis(ethene-2,1-diyl))bis(1,3,3-trimethyl-3H-indol-1-ium) iodide (3) and 2,2’-((1E,1′E)-(6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diyl)bis(ethene-2,1-diyl))bis(1,1,3-trimethyl-1H-benzo[e]indol-3-ium) iodide (4) were designed and synthesized by ethylene bridging of the N-substituted indolium salts and the Tröger’s Base (TB) framework. The probes exhibited a longer absorption and emission wavelength and the emission wavelength of them in dichloromethane (DCM) was more than 600 nm, performed a red fluorescence. All of the probes could work on the extreme acidic and the extreme alkaline environments and showed a good liner response in the working pH range. Especially, 2 and 4 were soluble in water and manifested a good pH sensing in a water system. Also, ¹H NMR analysis illustrated how these dyes worked as the pH-sensitive fluorescence probes. In addition, they performed excellent reversibility, high selectivity and good photostability.     

Synthesis and evaluation of polyimides derived from spirobisindane dietheranhydride

Polyimides derived from 5,5′-[(2,2′,3,3′-tetrahydro-3,3,3′,3′-tetramethyl-1,1′-spirobi[1H-indene]-6,6′-diyl)bis(oxy)]bis-1,3-isobenzofurandione (spirobisindane dietheranhydride, SBIDA) and 20 plus aromatic diamines were prepared. The weight percentage of cyclic contaminants in each polyimide, estimated by gel permeation chromatography, ranges from 4 to 25%. The amount of cyclics formed in each polyimide depends on the distance and spatial orientation of the two amino groups on the aromatic diamines as well as the rigidity of the diamines. The formation of SBIDA-containing polyimide was found to be catalyzed by alkali metal ions even when the reaction was conducted in m-cresol. Thermal stability and glass transition temperature of those SBIDA-derived polyimides were examined with thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). Two promising compositions were scaled up and their mechanical properties were obtained. © 1993 John Wiley & Sons, Inc.     

Regioselective Transformations of 2′,3′-Seconucleosides into Anhydro Structures and Chiral Crown Ethers

Intramolecular cyclisation of properly protected and activated derivatives of 2′,3′-secouridine ( = 1-{2-hydroxy-1-[2-hydroxy-1-(hydroxymethyl)ethoxy]-ethyl}uracil; 1 ) provided access to the 2,2′-, 2,3′-, 2,5′-, 2′,5′-, 3′,5′-, and 2′,3′-anhydro-2′,3′-secouridines 5, 16, 17, 26, 28 , and 31 , respectively (Schemes 1–3). Reaction of 2′,5′-anhydro-3′-O-(methylsulfonyl)- ( 25 ) and 2′,3′-anhydro-5′-O-(methylsulfonyl)-2′,3′-secouridine ( 32 ) with CH₂CI₂ in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene generated the N(3)-methylene-bridged bis-uridine structure 37 and 36 , respectively (Scheme 3). Novel chiral 18-crown-6 ethers 40 and 44 , containing a hydroxymethyl and a uracil-1-yl or adenin-9-yl as the pendant groups in a 1,3-cis relationship, were synthesized from 5′-O-(triphenylmethyl)-2′,3′-secouridine ( 2 ) and 5′-O,N⁶-bis(triphenylmethyl)-2′,3′-secoadenosine ( 41 ) on reaction with 3,6,9-trioxaundecane-1,11-diyl bis(4-toluenesulfonate) and detritylation of the thus obtained (triphenylmethoxy) methylcompound 39 and 43 , respectively (Scheme 4).     

Bisthiourea: thermal and structural investigation

Bisthiourea derivatives 1,1′-(ethane-1,2-diyl)bis(3-phenylthiourea), 1,1′-(propane-1,3-diyl)bis(3-phenylthiourea), and 1,1′-(butane-1,4-diyl)bis(3-phenylthiourea) have been synthesized and characterized by IR, ¹H NMR, and ¹³C NMR. Suitable crystals of 1,1′-(propane-1,3-diyl)bis(3-phenylthiourea) were grown for single-crystal X-ray analysis and from the data it was observed that they organize into the P-1 space group. The thermal decomposition of these compounds has been studied by TG–DSC.     

Photochemische reaktionen von übergansmetall-olefinkomplexen: III. [4 + 6]-cycloaddition konjugierter diene an hexacarbonyl-μ-η6:6(-1,1′-bi(2,4,6-cycloheptatrien-1-yl)dichrom(O)

UV irradiation of hexacarbonyl-μ-η^6:6-1,1′-bi(2,4,6-cycloheptatrien-1-yl)dichromium(O) (I) in THF in the presence of 1,3-butadiene (A), E-1,3-pentadiene (B) and EE-2,4-hexadiene (C) causes preferentially a twofold [4 + 6]-cycloaddition and formation of the hexacarbonyl-μ-2–5 : 8.9-η-2′–5′ : 8′,9′-η-11,11′-bi(bicyclo-[4.4.1]undeca-2,4,8-trien-11-yl)dichromium(O) complexes (IVA–IVC). Partial decomplexation after the first [4 + 6]-cycloaddition yields isomeric tricarbonyl-2–5:8,9-η- (IIA–IIC) and tricarbonyl-2′–7′-η-{11-(2′,4′,6′-cycloheptatrien-1′-yl)bicyclo[4.4.1]undeca-2,4,8-triene}chromium(O) complexes (IIIA–IIIC). With 2,3-dimethyl-1,3-butadiene (D) mainly dicarbonyl-2–6 : 2′–4′-η-{1-(2′,3′-dimethyl-3′-buten-1′,2′-diyl)-7-(8″,9″-dimethylbicyclo[4.4.1]undeca-2″, 4″,8″-trien-11″-yl)cyclohepta-3,5-dien-2-yl}chromium(O) (VD) besides small amounts of pentacarbonyl-μ-2–6 : 2′–4′-η-2″–7″-η-{1-(2′,3′-dimethyl-3′-buten-1′,2′-diyl)-7-(2″, 4″,6″-cycloheptatrien-1″-yl)cyclohepta-3,5-dien-2-yl}dichromium(O) (VID) and tricarbonyl-2′-7′-η-{11-(2′,4′,6′-cycloheptatrien-1′-yl)-8,9-dimethyl-bicyclo[4.4.1]undeca-2,4,8-triene}-chromium(O) (IIID) is obtained. VD adds readily CO to yield tricarbonyl-2–5 : 8,9-η-11,11′-bi(8,9-dimethyl-bicyclo[4.4.1]undeca-2,4,8-trien-11-yl)chromium(O) (VIID). Finally D adds to VID under formation of pentacarbonyl-μ-2–6 : 2′–4′-η-2″–5″ : 8″,9″-η-{1-(2′,3′-dimethyl-3′-buten-1′,2′-diyl)-7-(8″,9″-dimethyl-bicyclo[4.4.1]- undeca-2″,4″,8″-trien-11″-yl)cyclohepta-3,5-dien-2-yl}dichromium(O) (VIIID). From IVA–IVC the hydrocarbon ligands (IXA–IXC) can be liberated by P(OCH₃)₃ in good yields. The structures of the compounds IIA–IXC were determined by IR     

Synthesis and characterization of tetra-armed-thiosemicarbazone and its salen/salophen capped transition metal complexes: Investigation of their thermal and magnetic properties

In this work, we aimed to synthesize and characterize a novel tetra-directional ligand, (2E,2′E)-2,2′-((((2-(1,3-bis(4-((E)-(2-carbamothioylhydrazono)methyl)phenoxy)propan-2-ylidene)propane-1,3-diyl)bis(oxy))bis(4,1-phenylene))bis(methanylylidene))bis(hydrazinecarbothioamide) (5), including thiosemicarbazone group and its novel tetra-directional-tetra-nuclear Schiff base complexes. For this purpose, we used 1,4-dibromo-2,3-bis(bromomethyl)but-2-ene (2) as starting material. 4,4′-((2-(1,3-Bis(4-formylphenoxy)propan-2-ylidene)propane-1,3-diyl) bis(oxy))dibenzaldehyde (3) was synthesized by the reaction of an equivalent 1,4-dibromo-2,3-bis(bromomethyl)but-2-ene (2) and 4 equivalents of 4-hydroxybenzaldehyde. Then, compound 5 was synthesized in high yield (86%) by a condensation reaction of compound 3 with thiosemicarbazide (4). Finally, four novel tetra-nuclear Cr(III) or Fe(III) complexes of compound 5 were synthesized. The synthesized compounds were characterized using elemental analyses, ¹H NMR, Fourier transform–infrared spectrometry, liquid chromatography–mass spectrometry (ESI⁺), and thermal analyses. The metal ratios of the prepared complexes were determined using an atomic absorption spectrophotometer. We also investigated their effects on the magnetic behaviors of [salen, salophen, Cr(III)/Fe(III)] capped complexes. The complexes were found to be low-spin distorted octahedral Fe(III) and distorted octahedral Cr(III), all bridged by thiosemicarbazone.     

77Se NMR study of some organic selenium compounds formed in the selenium dioxide oxidation of ketones

⁷⁷Se NMR chemical shifts and ¹J(SeC) coupling constants were measured for nine organic selenium compounds: 4,5,6,7-tetrahydro-,4′,4′,6,6-tetramethylspiro[1,3-benzoxaselenole-2,1′-cyclohexane]-2′,4,6′-trione and closely related derivatives, bis(2-hydroxy-4,4,6,6-tetramethyl-3-oxo-1-cyclohexenyl) selenide and derivatives, and 1,5,5-trimethyl-7-selenabicyclo[2.2.1]heptane-2,3-dione. The chemicalshifts ranged from ?107 to 595 ppm from the external dimethyl selenide standard. The bridged selenabicyclic compound showed a small coupling constant (42 Hz).     

Synthesis of 2′-deoxyguanosine containing a N2-polyamine

The synthesis of benzylated N²-(4,7,10,13-tetraazatridec-1-yl)-2′-deoxyguanosines 4 was accomplished by a key nucleophilic reaction of the novel unsymmetrical polyamine 2 , with 3′,5′-O-(tetraisopropyldisiloxane-1,3-diyl)-2-chloro-2′-deoxyinosine ( 1 ).     

Solvent effects on the three-photon absorption cross-section of a highly conjugated fluorene derivative

Herein, we report the study of the three-photon absorption cross-section dependence on solvents parameters for a highly conjugated organic dye, 2,2'-(4,4'-(1E,1'E)-2,2'-(9,9-didecyl-9H-fluorene-2,7-diyl) bis(ethene-2,1-diyl)bis(4,1-phenylene))dibenzo[d]thiazole (A-pi-pi-pi-A). The three-photon absorption cross-section was measured for this organic dye in solution in four different solvents with polarity function, Deltaf between 0.162 and 0.247. The experiments show how the solvent's reorientation of the electrons and polarity contribute to the 3PA cross-section. Multiphoton-absorption experiments of A-pi-pi-pi-A in all four different solvents were performed with a tunable OPG pumped by a 25 picosecond Nd-YAG laser.