二茂铁-噻吩和联噻吩桥连吡啶盐类化合物的合成与电化学性质

设计并合成了3个二取代和三取代的二茂铁-噻吩、二茂铁-联噻吩吡啶盐类化合物： 碘化(E,E)-N-甲基-2,4,6-三{2-[5-(2-二茂铁乙烯基)噻吩-2-基]乙烯基}吡啶盐、 碘化(E,E)-N-甲基-2,6-二{2-[5’-(2-二茂铁乙烯基)-2,2’-联噻吩-5-基]乙烯基}吡啶盐、碘化(E,E)-N-甲基-2,4,6-三{2-[5’-(2-二茂铁乙烯基)-2,2’-联噻吩-5-基]乙烯基}吡啶盐。初步研究了这些化合物的电化学性质,结果表明,该类多取代二茂铁吡啶盐具有很好的氧化-还原可逆性,是潜在的电化学分子材料。     

含电子给体乙炔二茂铁化合物的光谱及电化学性质

合成了三种含电子给体乙炔基桥连二茂铁化合物Fc—C≡C—Ph—(p-OMe)(3a),Fc—C≡C—Ph—(p-NMe2)(3b)与Fc—C≡C—Ph—(p-NPh2)(3c),并对其结构、光化学及电化学性质进行了表征.吸收光谱表明,所有化合物在可见光区400-550nm都可归属为Fe(II)→Cp—C≡C—Ph—(p-R)(Cp为环戊二烯基)的金属到配体的电荷跃迁(MLCT)光谱,同时检测到3a与3c氧化态在近红外区(分别位于946与1044nm)可归属为Cp—C≡C—Ph—(p-R)→Fe(III)的配体到金属的电荷跃迁(LMCT).电化学测试结果表明,三种化合物都有稳定的Fc+/Fc可逆氧化还原电位,且3b与3c还出现Ph—NR2的氧化电位.3b对质子表现出光及电化学敏感性,随着质子的加入,其MLCT光谱红移,Fc+/Fc电位正移,而Ph—NR2+/Ph—NR2峰消失.     

A Conjugated Copolymer Bearing Imidazolium-based Ionic Liquid:Electrochemical Synthesis and Electrochromic Properties

An imidazolium-based ionic liquid(IL) modified triphenylamine derivative,namely 1-(4-((4-(diphenylamino)benzoyl) oxy)butyl)-3-methyl imidazole tetrafluoroborate(TPAC_6 IL-BF_4),was designed and synthesized,and further applied with 3,4-ethylene dioxythiophene(EDOT)to prepare conjugated copolymer P(EDOT:TPAC_6 IL-BF_4) via electrochemical polymerization.The cyclic voltammetry curves show that the copolymer P(EDOT:TPAC_6 IL-BF_4) possesses two pairs of redox peaks,which should be ascribed to the redox behaviors of EDOT and triphenylamine.The ultraviolet-visible(UV-Vis) absorption spectrum of P(EDOT:TPAC_6 IL-BF_4) exhibits one maximum absorption peak at 580 nm and a small shoulder characteristic peak at 385 nm under neutral state which are assigned to π-π~* conjugated structure of EDOT and triphenylamine.After being applied at the positive voltage,the copolymer color changes from dark blue to light blue,which is close to the color of poly(3,4-ethylenedioxythiophene)(PEDOT).Surprisingly,the copolymer P(EDOT:TPAC_6 IL-BF_4) shows shorter switching time of 0.37 s,0.30 s at 580 nm and 0.38 s,0.45 s at 1100 nm compared with PEDOT.It is more intriguing that the copolymer P(EDOT:TPAC_6 IL-BF_4) exhibits electrochromism even in free supporting electrolyte.The results confirm that the existence of imidazolium-based ionic liquid has an improvement on the ion diffusion properties and the switching time of conjugated polymer,which may provide a potential direction for the preparation of high-performance electrochromic materials.     

Ferrocenes with a Persulfurated Cyclopentadienyl Ring: Synthesis,Structural Studies,and Optoelectronic Properties

Persulfurated arenes are a fascinating class of functional molecules with a wide range of potential applications. Ferrocenes are also a multifaceted class of aromatic compounds that can easily be finetuned for an enormous variety of desired properties. A combination of both substance classes might yield an even wider field of applications. Herein, we describe the synthesis of two ferrocenes with one persulfurated cyclopentadienyl ring [C₅(SR)₅], with R=Me or Ph, together with their crystal structures, optical, and electrochemical properties. Both crystal structures show significant intramolecular sulfur-iron interactions as well as weak intermolecular sulfur– contacts. Cyclovoltammetry of the [C₅(SPh)₅] compound shows a high oxidation potential of 651 mV vs. FcH/FcH⁺.     

基于3,4-二烷氧基噻吩的D-A-D型有机共轭分子的合成及其光学和电化学性能

基于Wittig反应合成了新型D-A-D型有机半导体材料——双(2-乙烯基-3,4-二烷氧基噻吩)-对-2,5-二苯基-1,3,4-噁二唑[(3,4DAOTV)2-OXD],用核磁共振氢谱(1HNMR)、傅里叶变换红外(FTIR)光谱、高效液相色谱(HPLC)和元素分析法(EA)对化合物的结构进行分析和表征.用紫外-可见(UV-Vis)光谱、荧光(PL)光谱及电化学分析研究其光学和电化学性能.在氯仿溶液中,各化合物的紫外最大吸收波长(λmabasx)在382-383nm之间,光学带能隙在2.92-2.97eV之间,荧光最大发射波长在448-452nm之间,发出明亮的青色光,荧光量子产率可达36.8%-37.6%;在固体薄膜状态下,各化合物于513-516nm处发射出亮蓝绿色光.循环伏安法研究显示:三种大π共轭分子在正、负向区域均表现出明显的氧化、还原现象.其中,5.65-5.70eV的电离势(Ip),与噻吩类有机半导体材料的空穴传输特征相符;电子亲和势(Ia)在2.74-2.88eV之间,与有机电子传输材料的特性相近,这利于电子从阴极的注入和传输.理论计算结果表明,该D-A-D型共轭分子共平面性好和电荷离域程度高,对光电功能材料的分子界面组装、载流子的有效传输和器件量子效率的提高十分有利.     

Reactive Conjugated Polymers: Synthesis,Modification, and Electrochemical Properties of Polypentafluorophenylacetylene (Co)Polymers

(Co)Polymers containing pentafluorophenylacetylene (F₅PA) have been prepared for the first time mediated by [Rh(nbd)Cl]₂/NEt₃ to give materials with properties typical of poly(phenylacetylene)s prepared with this catalyst/co‐catalyst combination. It is demonstrated that the F₅PA repeat units in these new (co)polymers serve as convenient reactive species for post‐polymerization modification with thiols via para‐fluoro aromatic nucleophilic substitution reactions to give an entirely new family of novel thioether‐functional polyene materials accompanied by absorption maxima shifts of up to 130 nm. Finally, the electrochemical properties of these new fluorinated polyene materials are briefly examined and the distinct difference in behavior of the F₅PA homopolymer versus polyphenylacetylene, copolymers, and functional derivatives is highlighted.

     

共轭二茂铁席夫碱配合物的制备和电化学性质研究

合成了2个共轭二茂铁席夫碱配合物，用元素分析、红外光谱、紫外光谱、核磁共振等对它们进行了表征及电化学性质 研究，并用X射线衍射测定了它们的晶体结构。配合物1存在反演中心，其晶体属单斜晶系，P2₁/c空间群。晶体学数据为：a=1.148 5(2) nm，b=0.857 75(17) nm，c=1.194 4(2) nm，β=99.980(5)°,V=1.158 8(4) nm³,Z=2，μ=1.499 mm^-1,D_c=1.562 g·cm^-3，R₁=0.068 9，wR₂=0.128 0。     

新型苯并噁唑基吡啶盐的合成及其线性光学性质

以邻氨基苯酚和对甲基苯甲酸为原料,多聚磷酸为溶剂,N₂保护下于220 ℃反应制得中间体L1; L1溴代得中间体L2; L2与三苯基膦反应得膦盐L3,L3与吡啶-3-甲醛通过Wittig反应制得中间体L4,再通过甲基化反应和阴离子置换合成了未见报导的化合物1~6,并利用¹H NMR, ¹³C NMR, FT-IR和HR-MS对化合物1~6的结构进行了表征。单晶结构测试表明:化合物1(CCDC: 1838541)的阳离子部分的平面性较好。紫外可见吸收光谱和荧光发射光谱结果表明：化合物1~6在不同极性溶剂中均具有良好的光学性质。     

可溶液加工p-n多臂结构共轭分子的设计合成与应用

设计合成了两种以p型苯基咔唑为核,n型苯并噻二唑衍生物为臂的p-n多臂结构共轭分子S1和S2.通过1H NMR,13C NMR,GC-MS/MALDI-TOF等表征了其化学结构,研究了其光物理性质、热力学性质、电化学性质及其电子结构等,并作为活性材料应用于制备有机太阳能电池器件.实验结果表明所得的p-n多臂结构共轭分子表现出良好的溶液加工性、较宽的光谱吸收、较窄的能隙和较高的开路电压等特性.     

新型噻咯共轭聚合物的合成及其光伏性能

噻咯(silole)是一类含硅的五元环二烯, 具有很好的电子亲和力、独特的聚集态诱导发光性质和优良的电致发光性能. 研究者发现将噻咯结构单元引入分子主链中, 能够获得具有特殊光电性能的聚合物材料. 本工作合成两种2,5位为二噻吩苯并噻二唑的新型噻咯单体, 通过与芴或硅芴双硼酸酯Suzuki偶联聚合, 制备四种主链型D-A(推-拉电子结构)共聚物PF-HSTBT, PF-HOSTBT, PSiF-HSTBT和PSiF-HOSTBT. 研究表明, 四种聚合物具有较好的吸收, 光学带隙均小于1.71 eV. 电化学分析测得四种聚合物的HOMO能级均小于-5.29 eV, 通过光学带隙计算得LUMO能级均高于-3.61 eV. 以四种聚合物分别作为电子给体材料, PC₆₁BM为受体材料, 制备了聚合物太阳能电池器件(PSCs). 由于聚合物PF-HOSTBT、PSiF-HOSTBT中的己氧基空间位阻较大, 分子平面规整性较差, 其最高光电转换效率分别为0.62%、0.83%; 而己基的空间位阻较小, 分子堆积紧密, 聚合物PF-HSTBT, PSiF-HSTBT的光伏性能较优, PSCs的最高光电转换效率分别为1.18%, 1.2%.     

含二乙炔类共轭聚合物的合成及性能研究

在以CuCl和四甲基乙二胺(TMEDA)作为催化剂和邻二氯苯作溶剂条件下,以二-(4-乙炔苯基)-4-辛氧基苯胺(M1)和3, 6-双(乙炔基)-N-辛基咔唑(M2)作为单体,通过Glaser-Hay氧化偶联反应合成了含有咔唑和三苯胺结构单元的聚芳烃二乙炔共轭聚合物.采用红外光谱、核磁共振谱、热失重分析、紫外吸收光谱和荧光光谱等方法对聚合物进行结构表征与性能测试.所得到的聚合物都溶于普通的有机溶剂(如四氢呋喃、二氯甲烷、氯仿、甲苯等).结果表明,聚合物具有优异的热稳定性,热失重5 %时,分解温度在400℃以上;在光激发的条件下,聚合物在二氯甲烷溶液中发射蓝光.     

Synthesis and Magnetic Properties of Conjugated Stable Polyradicals

Synthesis and magnetic properties of π-conjugated stable polyradicals bearing a polyacetylene backbone are described. 2,6-Di-tert-butyl-4-ethynylphenol (8) and 4-ethynylphenylhydrogalvinoxyl (9) are polymerized with W, Mo chloride or Rh complex to yield their polyacetylene derivatives with molecular weight of ca. 10⁴, while 2-ethynylphenalenone (10) gives only its oligomer. The polymers are soluble in common solvents and converted to the corresponding conjugated polyradicals via heterogeneous chemical oxidation using PbO₂ or alkaline K₃Fe(CN)₆. The polyradicals with extremely high spin concentration (up to 4.8 × 10²³ spins/monomer mol) are obtained by regulating the oxidative conditions. The polyradicals are quite stable in solution and even in the solid state because of resonance stabilization and/or a steric effect of the substituents. Magnetic interactions between the unpaired spins in the conjugated stable polyradicals are discussed.     

Synthesis and Physical Properties of Benzopyridazine-Based Conjugated Molecules

A series of novel organic conjugated molecules （5a--5d） comprising 2,3-benzopyridiazine as electron-with- drawing core and thiophene derivatives as electron-donating arms have been synthesized successfully in good yields. The ultraviolet-visible （UV-Vis） absorption spectra and fluorescence spectra of 5a--5d revealed that the optical properties are strongly influenced by the interactions between nitrogen and sulfur atoms in the conjugated backbone, as well as the position of the alkyl chains in the thiophene rings. The experimental results and theoretical calculation data clearly indicated that the band gap and the energy levels of LUMO and HOMO could be fine-tuned by the po- sition of alkyl chains in the thiophene rings. Thus, the structure-property correlation of this class of conjugated molecules can be well established.     

一种具有双光子活性的新型吡啶盐的合成、表征及性质

一种具有双光子活性的新型吡啶盐的合成、表征及性质;D-π-A吡啶盐; 三阶非线性光学特性; 单晶X射线衍射; Z扫描     

两种新型吡啶盐的合成，表征及双光子性质研究

本文报道了两种新的吡啶盐的合成，用元素分析、红外光谱、单晶X-射线衍射进行了表征。研究了它们的紫外光谱、荧光光谱和光限幅特性，发现它们的DMF溶液对1 064 nm皮秒脉冲激光表现出明显的光限幅特性。     

Synthesis,Optical, and Electrochemical Properties of the High‐Molecular‐Weight Conjugated Polycarbazoles

Summary: A kind of novel dibromocarbazole monomer bearing three alkyl chains was prepared. Two strategies were developed to improve the solubility and molecular weight of carbazole polymers. One was the polymerization of N‐octyl‐2,7‐bis(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)carbazole with the alkylated dibromocarbazole. Another one was the polymerization of N‐octyl‐2,7‐bis(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)carbazole with N‐octyl‐3,6‐dibromocarbazole. All the polymerizations were carried out under palladium‐catalyzed Suzuki polycondensation (SPC) conditions. Through using carbazole monomer bearing three alkyl chains to polymerize, we have successfully boosted the number‐average molecular weight of 2,7‐linked carbazole polymers from not more than 5 to 67 kDa. The high‐molecular‐weight polymers were obtained in high yields and displayed good solubility in common organic solvents. Their optical, electrochemical, and thermal properties were also reported.

Preparation of carbazole polymers by Suzuki polycondensation.     

Synthesis, Characterization and Two-Photon Absorption Properties of a Novel Pyridinium Salt

A novel pyridinium salt, 2,4-bis[p-(N,N-dimethylamino)styryll-N-metlayl pyridinium iodide (BMSPI) was synthesized and characterized by TG, ^1H NMR spectroscopy and elemental analysis, and the reaction process was studied by using ES-MS. When BMSPI was pumped by a pulsed 1064 nm, 50 ps laser beam, it manifests highly efficient TPA (Two-Photon Absorption) and up-conversion superradiance. The up-conversion efficiency was 6.0% at the pump energy of 4-6 mJ and the lifetime of two-photon fluorescence was measured as 59 ps.     

Ferrocenes conjugated with thiophene,carbazole, and pyrimidine fragments: Synthesis and properties

Russian Journal of Applied Chemistry - Ferrocenyl-containing chalcones containing π-excessive heterocyclic fragments capable of electrochemical polymerization (carbazole, thiophene,...     

间苯二甲酸酯为端基的非对称共轭树状体的合成及光学性质

以间苯二甲酸酯为端基, 采用收敛法经钯催化的Sonogashira偶联反应合成了1～3代非对称的共轭树状体, 利用¹H NMR, ¹³C NMR, 质谱和元素分析进行了结构表征. 该类型树状体的骨架以间位和对位分枝的苯乙炔为基础, 其显著特征是每个吸电子基团都与一个给电子的烷氧基直接共轭. 对其光学性质的初步研究显示, 随着代数的升高它们的UV/vis吸收边缘和最大荧光发射波长均发生了红移.