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.     

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.     

基于吩噻嗪供体的敏化染料的合成及其光电性质

以吩噻嗪为供体,设计并合成了具有D-A-π-A或D-π-A结构的有机敏化染料2-氰基-3-{5-[7-(10-己基吩噻嗪-3-基)-苯并[1,2,5]噻二唑-4-基]-2-噻吩基}-丙烯酸(CVBTP)和2-氰基-3-{5-[7-(10-己基吩噻嗪-3-基)-2-噻吩基}-丙烯酸(CVTP)。在结构表征的基础上,研究了结构变化对敏化染料的光物理性质、电化学性质和光伏性能的影响。结果表明,在染料CVTP的D-π-A结构链上插入受体苯并噻二唑单元,得到的具有D-A-π-A结构的染料CVBTP的带隙变小,共轭体系变大,光吸收性能得到明显提升。CVBTP、CVTP的HOMO能级分别为-4.83、-4.82eV,LUMO能级分别为-2.85、-2.28eV,均与常见电解质I-/I-3(-4.60eVvs vacuum)和TiO2导带能级(-4.40eVvs vacuum)相匹配,都可用作DSSCs的敏化染料,但与CVBTP相比,CVTP具有更适合的LUMO能级和较好的光伏性能。     

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     

一维取代聚噻吩的电子性能

报道了3种取代聚噻吩,3-己基聚噻吩(P3HT)、3,4-二戊基聚噻吩(P34PT)、3-辛氧基聚噻吩(P3OOT)的合成方法1、H-NMR测试结果及UV-Vis吸收光谱和荧光光谱分析结果。用密度泛函方法计算了无取代噻吩、3-乙基噻吩、3,4-二乙基噻吩、3-乙氧基噻吩二聚体的电子性能。随聚合度的提高,聚合物能隙变窄。无取代噻吩二聚体的能隙为4.216 eV,重复单元长度为0.392 7 nm;乙基取代噻吩二聚体的能隙为4.733 eV,重复单元长度为0.393 9 nm;乙氧基取代噻吩二聚体的能隙为3.890 eV,重复单元长度为0.390 8 nm;双乙基取代噻吩二聚体的能隙为5.168 eV,重复单元长度为0.392 5 nm。理论变化规律与实验结果基本一致。     

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.     

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%。     

D-π-A型共轭聚合物的合成及其光伏性能

设计合成了3种主链相同、侧基不同的Donor(D)-π-Acceptor(A)型共轭聚合物:聚[(4,8-二辛氧基苯[1,2-b;3,4-b]二噻吩)-(9-(4-氰基苯基)-9H-咔唑)](PBDTCz-CN)、聚[(4,8-二辛氧基苯[1,2-b;3,4-b′]二噻吩)-(9-(4-醛基苯基)-9H-咔唑)](PBDTCz-CHO)和聚[(4,8-二辛氧基苯[1,2-b;3,4-b]二噻吩)-(9-(4-硝基苯基)-9H-咔唑)](PBDTCz-NO_2)。通过调变侧基上的受体基团,比较了氰基、醛基、硝基对聚合物光学和电学性能的影响,讨论了影响聚合物光电转换效率的主要因素。3种聚合物的光学带隙和线性吸收系数依次分别为2.32 eV,152.0 L/(g·cm);2.43 eV,58.5 L/(g·cm)和2.25 eV,85.5 L/(g·cm)。在这些聚合物中,彼此间的最高占据分子轨道(HOMO)能级差距很小,PBDTCz-NO_2的最低未占据分子轨道(LUMO)能级最低(-3.38eV)。在100 W/m~2模拟太阳光的照射下,基于这些聚合物的光伏器件(器件结构:ITO/PEDOT:PSS/Polymer:[70]PCBM(1:2)/Ca/A1)的光电转换效率分别为0.44%(PBDTCz-CN)、0.001 8%(PBDTCz-CHO)和0.23%(PBDTCz-NO_2)。低的光电转换效率主要归因于低的短路电流,而影响短路电流的主要原因有自身吸光性能的限制和弱的π-π堆砌作用。     

蒽类衍生物的电荷传输性质

以具有较高迁移率的对称取代类蒽的衍生物{2,6-二[2-(4-戊基苯基)乙烯基]蒽,DPPVAnt;2,6-二-噻吩蒽,DTAnt;2,6-二[2-己基噻吩]蒽,DHTAnt}为研究对象,采用密度泛函理论的B3LYP方法,在6-31G(d)的基组水平上研究了三种蒽类衍生物的分子结构、电子结构、重组能和电荷传输积分,采用Einstein关系式计算了室温下的载流子迁移率,并与蒽的相关计算结果进行了比较.DPPVAnt是较好的空穴传输材料,其空穴迁移率为0.49cm2·V-1·s-1;DHTAnt有利于电子传输,其电子迁移率为0.12cm2·V-1·s-1;而DTAnt是一种较好的双极性材料,其空穴迁移率和电子迁移率分别为0.069和0.060cm2·V-1·s-1.计算得到的迁移率与实验结果处于同一数量级.三种蒽类衍生物的电子重组能与蒽的相近,而空穴重组能均大于蒽的空穴重组能,大小顺序为蒽DPPVAntDTAntDHTAnt.这与计算的迁移率结果不一致,说明分子的堆积结构决定材料的电荷传输性质.     

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.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.