窄能隙共轭聚合物:聚[(3-烷基)噻吩-2,5]-取代苯甲烯衍生物的合成与表征

合成了3-丁基噻吩和3-辛基噻吩,并分别与对硝基苯甲醛和对二甲氨基苯甲醛进行聚合反应得到了具有极低能隙的聚(3-丁基噻吩)对硝基苯甲烯(PBTNBQ)、聚(3-丁基噻吩)对二甲氨基苯甲烯(PBTDMABQ)和聚(3-辛基噻吩)对二甲氨基苯甲烯(POTDMABQ).采用红外光谱、核磁共振氢谱和紫外-可见吸收光谱确认了产物的结构,发现中间产物聚(3-烷基)噻吩取代苯甲烷衍生物中存在部分醌化产物.根据E_g与入射光子能量hν的关系,采用2种模型计算了3种聚合物薄膜的光学禁带宽度为PBTNBQ1.63,1.84eV;PBTDMABQ1.44,1.75eV和POTDMABQ1.32,1.69eV,属窄能隙共轭聚合物.     

含五氟苯的噻吩并吡咯二酮苯并二噻吩共轭聚合物的合成及其性能

以3,4-噻吩二甲酸和五氟苯胺为起始原料,经酰化、缩合和NBS溴代反应制得2,5-二溴-5-五氟苯基噻吩［3,4-c］吡咯-4,6-二酮(2); 2经两步反应制得2-溴-2,5-二噻吩-5-五氟苯基噻吩［3,4-c］吡咯-4,6-二酮(4);以苯并二噻吩衍生物（BDT-1和BDT-2）为给体单元,2或4为受体单元,分别经Stille偶联缩聚反应合成了3个含五氟苯的噻吩并吡咯二酮-苯并二噻吩共轭共聚物(5a~5c),其结构和性能经¹H NMR, ¹³C NMR, UV-Vis, TGA和循环伏安法表征。结果表明：5a, 5b和5c的最大吸收峰分别位于559 nm, 559 nm和547 nm,光学带隙分别为1.70 eV, 1.73 eV, 1.68 eV(薄膜)和1.84 eV, 1.83 eV, 1.81 eV(甲苯);失重5%的温度为307～325 ℃; 5a~5c的起始氧化电位和起始还原电位分别为1.14 V, 1.18 V, 1.03 V和-0.67 V, -0.67 V, -0.70 V; HOMO和LUMO能级分别为-5.54 eV, -5.58 eV, -5.43 eV和-3.73 eV, -3.73 eV, -3.70 eV。     

3-烷基噻吩交替共聚物的合成及其电化学性质

通过Heck偶联法合成了4种3-烷基噻吩交替共聚物:聚(2,4-二乙烯基-3-己基噻吩-1,3,4-二唑)(P3HT-OXD)、聚(2,4-二乙烯基-3-辛基噻吩-1,3,4-二唑)(P3OT-OXD)、聚(2,4-二乙烯基-3-己基噻吩-吡啶)(P3HT-Py)和聚(2,4-二乙烯基-3-辛基噻吩-吡啶)(P3OT-Py). 用NMR、GPC等测试技术对其结构进行了表征. 采用循环伏安法、紫外-可见吸收光谱法研究了系列共聚物光电性能. 结果表明,随噻吩环3位取代烷基碳链的增长,聚合物电离能(Ip)减小,带隙(Eg)也随之变窄. 其中,P3OT-OXD的Eg比P3HT-OXD小0.11 eV,P3OT-Py的Eg比P3HT-Py小0.19 eV,在3-烷基噻吩聚合物主链上引入吸电子能力较强的二唑单元,可有效提高共聚物电子亲合能(Ea),对提高电子传输能力,改善电子与空穴注入平衡有积极作用.     

新型p-/n-交替3-烷基噻吩共聚物的合成及其光电性质的研究

通过Heck偶合法合成了四种新型p-/n-交替3-烷基噻吩共聚物：聚(2,4-二乙烯基-3-己基噻吩-1,3,4-噁二唑) (P3HT-OXD)、聚(2,4-二乙烯基-3-辛基噻吩-1,3,4-噁二唑) (P3OT-OXD)、聚(2,4-二乙烯基-3-己基噻吩-吡啶) (P3HT-Py)、聚(2,4-二乙烯基-3-辛基噻吩-吡啶) (P3OT-Py)。利用NMR、GPC等方法对结构进行了分析表征。采用循环伏安法、紫外－可见吸收光谱法对该系列共聚物的光电性能进行了研究,结果表明：随着噻吩环3位取代烷基碳链的增长,聚合物电离能（Ip）减小,带隙能（Eg）也随之变窄,其中,P3OT-OXD的Eg比P3HT-OXD小0.11ev,P3OT-Py的Eg比P3HT-Py小0.19eV;而在3-烷基噻吩聚合物主链上引入吸电子能力较强的噁二唑单元,可有效提高共聚物电子亲合能（Ea）,对提高电子传输能力,改善电子与空穴注入平衡有积极作用     

基于3,4-二氰基噻吩的宽带隙共轭聚合物的设计合成与光伏应用

利用3,4-二氰基噻吩(DCT)为电子受体单元,苯并双噻吩(BDT)为电子给体单元,并结合不同侧链取代的噻吩为π桥,设计合成了一系列新型宽带隙共轭聚合物:PB3TCN-C32、PB3TCN-C36、PB3TCN-C36-R以及PB3TCN-C40.这些聚合物具有较宽的光学带隙( 1.8 eV)、较深的最高占有分子轨道(HOMO)能级.与非富勒烯受体(IT-4F)结合制备了有机太阳电池器件,其中聚合物PB3TCN-C40实现了高达11.2%的能量转换效率(PCE),其开路电压(V_(oc))为0.92 V,短路电流密度(J_(sc))为18.9 mA cm~(-2),填充因子(FF)为0.64,是目前文献报道基于氰基噻吩类聚合物材料的最好结果.同时,该体系具有低至0.6 eV的能量损失.这些结果表明DCT是一种极具潜力的实现宽带隙、深HOMO能级共轭聚合物的构筑单元,有望实现更高能量转换效率的有机太阳电池.     

含磺酰基的二维醌式窄带隙共聚物的制备与性能

以噻并[3,2-b]噻吩为共轭侧基,苯并[1,2-b：4,5-b′]二噻吩和磺酰基取代的噻并[3,4-b]噻吩为共聚单元,在Pd₂(dba)₃-P(o-tol)₃催化下,经Stille缩聚反应合成了二维窄带隙醌式共聚物(PTTBDT-TTS, 1),其结构和性能经¹H NMR,元素分析,凝胶渗透色谱(GPC), UV-Vis, TGA和循环伏安法表征。结果表明：1具有良好的成膜性和热稳定性;1在300~800 nm对太阳光有较强吸收,HOMO能级为-5.45 eV;倒置光伏器件(1/PC-61-BM)的开路电压为0.95 V,能量转换效率约为1.07%。     

含均苯四甲酸二酰亚胺受体单元的共轭高分子的合成及其在有机太阳能电池上的应用

通过Stille反应合成了一系列含有均苯四甲酸二酰亚胺受体单元的共轭聚合物P1～P7.该系列聚合物在常见有机溶剂中溶解性良好,在370～600 nm范围内有较强吸收.通过循环伏安法测量其LUMO能级范围在-3.66～-3.90 eV之间,HOMO能级在-5.25～-6.17 eV之间,在同类分子中接近最低值.通过改变主链中噻吩单元的数量和给电子单元,可以调节分子的能隙,使其电化学能隙在2.45～1.55 eV范围内变化.将含均苯四甲酸二酰亚胺受体单元的P1～P7应用于有机太阳能电池中,作为给体材料与PC61BM共混制成本体异质结聚合物电池,器件开路电压普遍较高.其中基于均苯四甲酸二酰亚胺与二噻吩并噻咯的聚合物P7的器件,在AM 1.5 G,86 mW/cm2光照条件下,开路电压为0.72 V,短路电流为1.22 mA/cm2,能量转换效率为0.27%.     

烷基和烷氧基取代聚噻吩的合成、表征与光电性能

Fe(Ⅲ )氧化催化法合成了 4种聚噻吩衍生物 ,3 十二烷基聚噻吩 (Pat12 ) ,3 辛氧基聚噻吩 (Paot8) ,3,4 二 (十二烷基 )聚噻吩 (Pat12 12 )和 3 (十二烷基 )噻吩 3 (辛氧基 )噻吩共聚物 (CoPt12 o8) .发现这些衍生物易溶于多种常用有机溶剂 .用GPC法测定了各聚合物分子量 ,用1 H NMR法表征了各聚合物化学结构 .对比研究了这些聚合物紫外 可见吸收性能 ,光致发光性能和能隙 .对其电致发光性能进行测定的结果 ,得到了Pat12 ,Pat12 12和Paot8的电致发光光谱 .发射峰分别为 6 70nm ,5 6 0nm和 6 4 0nm .发光颜色分别为红色 ,黄色和红橙色 .聚合物的光电性能与主链电子结构有密切关系 .探讨了取代基种类和数量对聚合物能带结构 ,光电性能的影响 .     

羟甲基和碘甲基取代的3,4-亚乙基二氧噻吩衍生物及其选择性酯化与醚化

羟甲基或碘甲基取代的3,4-亚乙基二氧噻吩(EDOT)衍生物与含氰乙基或羧酸基的四硫代富瓦烯(TTF)衍生物通过酯化或醚化反应可生成EDOT-TTF类型的化合物.在此过程中发现,由3,4-二羟基噻吩-2,5-二羧酸甲酯(1)与环氧溴丙烷经醚化反应生成的关环产物是一个由3,4-二氧-羟甲基乙基噻吩-2,5-二羧酸甲酯(2)与3,4-二氧-2’-羟基亚丙基噻吩-2,5-二羧酸甲酯(2’)组成的混合物,两者很难用常规手段分离.由(2+2’)衍生的2,5-二羧酸甲酯-3,4-二氧-碘代甲基亚乙基噻吩(3)和3,4-二氧-碘代亚丙基噻吩-2,5-二羧酸甲酯(3’)以及3,4-二氧-羟甲基亚乙基噻吩(4)与3,4-二氧-2’-羟基亚丙基噻吩(4’)与2-氰乙基硫-3-甲基硫-6,7-二(正己基硫)-四硫代富瓦烯(TTF-1)或2-羧甲基硫-3-甲基硫-6,7-二(正己基硫)-四硫代富瓦烯(TTF-3)进行醚化或酯化反应表现出了高度的选择性,只有3能与TTF-1反应生成结构单一的EDOT-TTF 1.同样只有4能与TTF-3反应生成结构单一的EDOT-TTF 2.     

取代基结构对聚[(3-烷基)噻吩-2,5]-取代苯甲烯衍生物三阶非线性光学性能的影响

采用3-烷基噻吩与对硝基苯甲醛和对二甲氨基苯甲醛的聚合反应得到了5种聚(3-烷基)噻吩取代苯甲烯衍生物:聚(3-丁基)噻吩对硝基苯甲烯(PBTNBQ)、聚(3-己基)噻吩对硝基苯甲烯(PHTNBQ)、聚(3-丁基)噻吩对二甲氨基苯甲烯(PBTDMABQ)、聚(3-己基)噻吩对二甲氨基苯甲烯(PHTDMABQ)和聚(3-辛基)噻吩对二甲氨基苯甲烯(POTDMABQ).计算其光学禁带宽度分别为PBTNBQ(1.82eV),PHTNBQ(1.85eV),PBTDMABQ(1.71eV),PHTDMABQ(1.78eV)和POTDMABQ(1.67eV).利用简并四波混频技术测量了5种聚合物薄膜的三阶非线性极化率,分别为1.74×10^-8,1.82×10^-8,5.62×10^-9,8.64×10^-9和1.22×10^-8esu,均具有较大的三阶非线性光学性能.针对取代基结构对聚(3-烷基)噻吩取代苯甲烯衍生物的三阶非线性光学性能的影响从分子内极化程度和主链电子的离域程度两个方面进行了讨论.     

Preparation and properties of a novel polythiophene,poly[(3‐hexyliminomethyl)thiophene] with a high regioregularity

Poly[(3‐hexyliminomethyl)thiophene]s (P3HITs) were synthesized from the polymerizations of 2,5‐dibromo‐(hexyliminomethyl)thiophene and 5‐bromo‐2‐iodo‐3‐(hexyliminomethyl)thiophene by Grignard metathesis method. The corresponding P3HITs with low regioregularity (70%) and high regioregularity (95%) were obtained, respectively. UV–vis and photoluminescence spectra of P3HIT were dependent on the regioregularity and solvent polarity. By hydrolysis of the imino groups in the side chains under acidic conditions, P3HIT was successfully converted into the polythiophene (P3TCHO) having aldehyde groups. This transformation was also performed facilely by exposing the P3HIT film to HCl gas to give the polythiophene having aldehyde moiety. The reverse way from aldehyde to imine was also successfully demonstrated by treating the film with triethylamine vapor. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and properties of novel oligothiophenes surrounded by bicyclo[2.2.2]octene frameworks

Novel oligothiophenes surrounded by bicyclo[2.2.2]octene (abbreviated as BCO) frameworks ranging from dimer to hexamer, 1(nT) (n = 2, 3, 4, 6), were prepared, and their structures and electronic properties were investigated. Dimer 1(2T) was synthesized by oxidative coupling of the 2-lithiated monomer generated from 4,5-BCO-annelated 2-bromothiophene 8 with CuCl2 in 76% yield. Trimer 1(3T) and tetramer 1(4T) were synthesized by Stille coupling of 2,5-dibromo-3,4-BCO-annelated thiophene 4 and of the 5,5'-dibromo derivative of bis(3,4-BCO-thiophen-2-yl) 10 with 2-stannylated 4,5-BCO-annelated thiophene 9 in 41% and 46% yield, respectively. Hexamer 1(6T) was synthesized by oxidative coupling of terthiophene 12, tris-annelated with BCO units, in 81% yield. X-ray crystallographic studies showed that the thiophene rings in 1(2T) and 1(3T) are rotated around the inter-ring C-C bond(s) with the C=C-C=C dihedral angles of -174.3(5) degrees for 1(2T) and -149.7(3) degrees and 34.4(3) degrees for 1(3T). In the crystal structures of 1(2T) and 1(3T), no pi-stacking was observed as expected from the steric effect of the BCO units. Theoretical calculations for 1(2T) and 1(3T) at the B3LYP/6-31G(d) level indicated that the annelation with BCO units either at the 2,3- or 3,4-positions of thiophene rings raises both the KS HOMO and LUMO levels. In the electronic absorption spectra of 1, the longest wavelength absorption band corresponding to the pi-pi transition is bathochromically shifted with the increase in absorption intensity as the number of thiophene rings increases, and the absorption of the polythiophene 1 with infinite length was predicted to be 419 nm. The cyclic voltammetry of 1 in CH2Cl2 at -78 degrees C (2T) or at room temperature (3T, 4T, 6T) showed two reversible oxidation waves, indicating that the radical cation and dication of 1 are stable under these conditions.     

Effect of side‐chain end groups on the optical,electrochemical, and photovoltaic properties of side‐chain conjugated polythiophenes

Three new side‐chain conjugated polythiophene derivatives, poly{3‐[2‐(3‐methoxy‐4‐octyloxy‐phenyl)‐vinyl]‐thiophene} (P3MOPVT), poly{3‐[2‐(3,5‐dimethoxy‐4‐octyloxy‐phenyl)‐vinyl]‐thiophene} (P3DMOPVT), and poly{3‐[2‐(3,4‐dioctyloxy‐phenyl)‐vinyl]‐thiophene} (P3DOPVT), were synthesized by Wittig‐Hornor reaction and GRIM method and compared with poly{3‐[2‐(4‐octyloxy‐phenyl)‐vinyl]‐thiophene} (P3OPVT) for investigating the effect of the end groups of the conjugated side‐chain on the properties of the polymers. Owing to the electron‐donating ability of methoxy groups, the visible absorption peaks of P3MOPVT and P3DMOPVT solutions and films become stronger and red‐shifted compared with P3OPVT. The electrochemical bandgaps of the four polymers are 2.15 eV for P3OPVT, 1.99 eV for P3MOPVT, 1.85 eV for P3DMOPVT, and 2.36 eV for P3DOPVT, respectively, which indicate that the electron‐donating ability of the methoxy end group on the conjugated side chain of P3MOPVT and P3DMOPVT and the large steric hindrance of the two octyloxy end groups on the conjugated side chain of P3DOPVT have obvious influence on the electrochemical properties of the side‐chain conjugated polythiophenes. Polymer solar cells were fabricated with a structure of ITO/PEDOT:PSS/Polymer:PCBM/LiF/Al. The best device, based on P3DMOPVT, shows a power conversion efficiency of 1.63% under the illumination of AM1.5, 80 mW/cm². © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4916–4922, 2006     

Synthesis and properties of polythiophenes with conjugated side‐chains containing carbon–carbon double and triple bonds

Two soluble side‐chain conjugated polythiophenes, poly{3‐[2‐(4‐octyloxy‐phenyl)‐vinyl]‐thiophene} (P3OPVT) and poly{3‐(4‐octyloxy‐phenylethynyl)‐thiophene} (P3OPET) have been synthesized successfully. In P3OPVT and P3OPET, substituted benzene rings are connected with the polythiophene backbone through trans carbon–carbon double bond and carbon–carbon triple bond, respectively. Absorption spectra of the P3OPVT and P3OPET both show two absorption peaks located in UV and visible region, respectively. The results of optical and electrochemical measurements indicate that the conjugated side‐chains can reduce the bandgap effectively. This type of side‐chain conjugated polythiophenes may be promising for the applications in polymer photovoltaic cells and field effect transistors. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2206–2214, 2006     

Electrochemical preparation of polythiophene via 2,5-bis(trimethylsilyl)thiophene

Electrochemical polymerization of 2,5-bis(trimethylsilyl) thiophene produced highly conducting films which showed infrared spectra, visible-near infrared absorption spectra, and cyclic voltammograms identical to films prepared from thiophene. Elemental analysis indicated that almost all silicon atoms were eliminated during the electrochemical polymerization. However, scanning electron microscopy showed a morphological difference between the films from 2,5-bis(trimethylsilyl)thiophene and from thiophene. The electrochemical polymerization of bis(2-thienyl)dimethylsilane, 1,2-bis(2-thienyl)tetramethyldisilane, and bis(2-thienyl)diphenylsilane also produced polythiophene films having unique morphologies quite different from the conventional ones. These findings indicate that these electrochemical procedures must be useful for preparation of new conjugated polymers. © 1992 John Wiley & Sons, Inc.     

Theoretical DFT and experimental Raman and NMR studies on thiophene, 3-methylthiophene and selenophene

The results of extended MO calculations using density functional theory (DFT) approximation supported by experimental Raman, ¹H and ¹³C NMR studies on thiophene are reported. Raman spectra of liquid thiophene were re-examined and the performance of a hybrid B3PW91 density functional was compared with the ab initio restricted Hartree–Fock (RHF) method. With the basis sets of the 6-311++G^** quality, the DFT calculated bond lengths, dipole moments and harmonic vibrations were predicted in a very good agreement with available experimental data.

Additionally, the results on thiophene were extended by calculations on 3-methylthiophene and selenophene. In this case, a significant change in geometry and charge distribution in thiophene ring due to a methyl group substituent or replacement of sulphur by selene atom was observed.

A linear correlation between the predicted harmonic vibrational frequencies (scaled using SQM method) and experimental ones for thiophene, selenophene and 3-methylthiophene was shown. The theoretically calculated spectra have satisfactorily reproduced the available experimental spectra for thiophene and selenophene.     

电化学聚合吡咯/噻吩导电共聚物纳米纤维阵列及其表征

导电聚合物因其具有良好的空气稳定性、电化学成膜性和导电性等特点,在二次电池、电色显示及固体电容器等方面都有诱人的应用前景.近年来人们研究导电聚合物的纳米结构时发现,由于超分子效应,纳米纤维中聚合物链会以平行于纤维轴向为优先取向,这种优先取向使导电聚合物纳米纤维的电导率比块材有极大提高.     

A facile route of polythiophene nanoparticles via Fe3+‐catalyzed oxidative polymerization in aqueous medium

We have demonstrated that unsubstituted thiophene can be polymerized by Fe³⁺‐catalyzed oxidative polymerization inside nanosized thiophene monomer droplets, that is, nanoreactors, dispersed in aqueous medium, which can be performed under acidic solution conditions with anionic surfactant. Besides, we proposed a synthetic mechanism for the formation of the unsubstituted polythiophene nanoparticles in aqueous medium. This facile method includes a FeCl₃/H₂O₂ (catalyst/oxidant) combination system, which guarantees a high conversion (ca. 99%) of thiophene monomers with only a trace of FeCl₃. The average particle size was about 30 nm, within a narrow particle‐size distribution (PDI = 1.15), which resulted in a good dispersion state of the unsubstituted polythiophene nanoparticles. Hansen solubility parameters were introduced to interpret the dispersion state of the polythiophene nanoparticles with various organic solvents. The UV–Visible absorption and photoluminescence (PL) spectrum were measured to investigate the light emitting properties of the prepared unsubstituted polythiophene nanoparticle emulsions. According to non‐normalized PL analysis, the reduced total PL intensity of the polythiophene nanoparticle emulsions can be rationalized by self‐absorption in a wavelength range less than 500 nm. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2097–2107, 2008     

Synthesis of trans‐dihydrodiol derivatives of phenanthro[3,4‐b]‐thiophene and phenanthro[4,3‐b]thiophene

The present study describes the synthesis of phenanthro[3,4‐b]thiophene (3) , phenanthro[4,3‐b]thiophene (4) and its potential dihydrodiol metabolites, trans‐6,7‐dihydroxy‐6,7‐dihydrophenanthro[3,4‐b]thiophene (5) and trans‐8,9‐dihydroxy‐8,9‐dihydrophenanthro[3,4‐b]thiophene (6) , trans–6,7‐dihydroxy‐6,7‐dihydro‐phenanthro[4,3‐b]thiophene (7) and trans‐8,9‐dihydroxy‐8,9‐dihydrophenanthro[4,3‐b]thiophene (8) from Suzuki coupled intermediates. The UV spectra of these dihydrodiols are presented. These spectra are useful tools for identifying these dihydrodiols among unknown metabolites of 1 and 2 produced in vitro or in vivo.     

3-取代和3,4-二取代噻吩的合成与表征

以噻吩、48% (m/m)氢溴酸水溶液、35% (m/m)过氧化氢水溶液、高纯氨、金属钠为原料合成了3-溴噻吩和3,4-二溴噻吩,3-溴噻吩和3,4-二溴噻吩分别以(dppp)NiCl2为催化剂合成了3-烷基噻吩和3,4-二烷基噻吩.3-溴噻吩以CuI, NaHSO4为催化剂合成了3-烷氧基噻吩,产率较高.并用核磁共振谱、质谱和元素分析方法进行了表征.