类杂芪染料分子第一超极化率的溶剂效应研究

从实验上证明了反式-(2-N-甲基吡咯基)-(4-N-甲基吡啶基)杂芪碘(MPPSI),反式-(2-吡咯基)-(4-N-甲基吡啶基)杂芪碘(PPSI),反式-(2-呋喃基)-(4-N-甲基吡啶基)杂芪碘(FPSI)和反式-(2-噻吩基)-(4-N-甲基吡啶基)杂芪碘(TPSI)在15种溶剂中的分子第一超极化率(β~χ~χ~χ)与给电子取代基的富电子性间的线性关系,得到了β~χ~χ~χ值与溶剂极性间的线性相关性,从以上两个线性相关中得到了溶剂极性影响类杂芪分子给/吸电子取代基的给/吸电子能力的溶剂系数δ~A和δ~D,以及分子内电荷转移对溶剂极性的敏感因子η。     

固态类杂芪分子一阶超极化率测定及溶剂效应

用溶致变色法研究溶剂对反式 (4 N ,N 二甲氨基 ) (4 N 甲基吡啶基 )杂芪碘 (DAPSI) ,反式 (2 N 甲基吡咯基 ) (4 N 甲基吡啶基 )杂芪碘 (MPPSI) ,反式 (2 吡咯基 ) (4 N 甲基吡啶基 )杂芪碘 (PPSI)、反式 (2 呋喃基 ) (4 N 甲基吡啶基 )杂芪碘 (FPSI)、反式 (2 噻吩基 ) (4 N 甲基吡啶基 )杂芪碘 (TPSI)和反式 (4 N 甲基吡啶基 )杂芪碘 (PSI)的分子一阶超极化率 (βxxx)的影响 ,揭示了溶剂极性 (ET(30 ) )与类杂芪染料的 βxxx值间很好的线性关系和影响规律 ,引入了溶剂化效应对待测化合物分子能级的影响与待测化合物分子间相互作用能级间存在等效能级的概念 ,从溶剂极性 (ET(30 )值 )与 βxxx值间的线性关系求出了在纯固态下类杂芪染料的 βsxxx值 ,及基态与第一激发态间跃迁能和最大吸收波长 .证明了MPPSI、PPSI、FPSI、TPSI和PSI在纯固态下的 βsxxx值与给电子取代基的富电子性间有很好的线性关系     

固态类杂芪分子一阶超极化率测定及溶剂效应

用溶致变色法研究溶剂对反式－（４－Ｎ,Ｎ－二甲氨基）－（４－Ｎ－甲基吡啶基）杂芪碘（ＤＡＳＰＩ）、反式、（２－Ｎ－比咯基）－（４－Ｎ－甲基吡啶基）杂芪碘３＊（ＭＰＰＳＩ）,反式－２（２－吡咯基）－２（４－Ｎ－比啶基）杂芪磺（ＰＰＳＩ）、反式－（２－呋喃基）－（４－Ｎ＿甲基吡啶基）杂芪碘（ＦＰＳＩ）、反式－（２－噻吩基）－（４－Ｎ－甲基吡啶基）杂芪磺（ＴＰＳＩ）和反式＿４－Ｎ－Ｌ在吡啶基）杂芪碘（Ｐ     

上转换荧光化合物DMSSB与CSSB的合成、结构与光物理性质

以苯并噻唑为电子受体,以双苯乙烯基为共轭桥链,分别以二甲基胺和咔唑为电子给体合成了2个新的有机化合物DMSSB(反式,反式-2-{4-[(4-N,N-二甲基胺)苯乙烯基]苯乙烯基}-1,3-苯并噻唑)和CSSB(反式,反式-2-{4-[(4-N-咔唑)苯乙烯基]苯乙烯基}-1,3-苯并噻唑).用X射线衍射方法测定了CSSB的晶体结构.用波长为800nm的激光激发时,DMSSB与CSSB在THF中分别发出强的上转换橙色(λ_max=589nm)和蓝绿色荧光(λ_max=488nm).2个化合物在不同溶剂中的光物理数据和理论计算结果表明,苯并噻唑基是一个很好的电子受体.     

两种新型有机激光染料的合成、结构和上转换 发光性质

合成了两个新的有机晶体：反式-4-[4'-(N-羟乙基-N-甲基胺基)苯乙烯基]-N-甲基吡啶对甲苯磺酸盐trans-4-[4'-(N-hydroxyethyl-N-methylamino)styryl]-N-methylpyridiniumtoluene-p-sulfonate(简称HMASPS)和反式-4-[4'-(N-羟乙基-N-乙基胺基)苯乙烯基]-N-甲基吡啶对甲苯磺酸盐trans-4-[4'-(N-hydroxyethyl-N-ethylamino)styryl]-N-methylpyridiniumtoluene-p-sulfonate(简称HEASPS)。用X射线衍射方法对这两个单晶进行了结构测定。测试了它们频率上转换荧光及激光性质。在1064nm的ps脉冲激光的激发下,HMASPS和HEASPS在溶液中均发出～625nm的上转荧光和激光,并且有可观的激光效率。     

纳米晶TiO2电极上半菁衍生物光敏染料

合成了具有不同共轭链长度的吡啶盐类及喹啉盐类半菁染料(E)-N-(4-磺酸丁基)-4-[2-(4-N, N-二甲基氨基苯基)乙烯基]吡啶鎓盐(P1)、(E)-N-(4-磺酸丁基)-4-[2-(4-N, N-二甲基氨基苯基)丁二烯基]吡啶鎓盐(P2)、(E)-N-(4-磺酸丁基)-4-[2-(4-N, N-二甲基氨基苯基)乙烯基]喹啉鎓盐(Q1)以及(E)-N-(4-磺酸丁基)-4-[2-(4-N, N-二甲基氨基苯基)丁二烯基]喹啉鎓盐(Q2).研究了它们的光物理性质，并将它们用作TiO2纳米晶电极的光敏化剂引入光电化学电池.与含有乙烯基共轭桥的染料P1和Q1相比，含有丁二烯基共轭桥的染料P2和Q2在甲醇和氯仿中的最大吸收均发生一定程度的红移，而且吸收光谱变宽.这两类染料都能很好地吸附于TiO2电极上.在比较了四个染料的吸收光谱、摩尔消光系数以及在TiO2电极表面的吸附量后，发现Q1具有最好的光电转化性质.     

一种新型α-甲醚基吡咯的合成

以乙酰乙酸苄酯(4)为原料, 经Knorr缩合制备了2,4-二甲基-3-丙酸甲酯基-5-羧酸苄酯基-1-氢吡咯 (2) 和2,4-二甲基-3-羧酸甲酯基-5-羧酸苄酯基-1-氢吡咯(3)。乙醚介质中,溴水氧化条件下,吡咯 (2) 发生自身缩合生成二吡咯甲烷 (7),吡咯 (3)无反应发生。在Pb(OAC)₄氧化条件下,当其浓度为吡咯 (3)浓度的2倍时,在80 ℃,吡咯 (3) 完全转华。所得产物经HCl甲醇溶液回流,以82%的产率制备了新型2-甲氧基甲基-3-羧酸甲酯基-4-甲基-5-羧酸苄酯基-1氢吡咯 (1)。吡咯(1)、(2)、(3)及二吡咯(7)的结构用核磁、元素分析、质谱和红外等测试技术进行了表征。吡咯(1)的构建对进一步研究吡咯构效关系具有一定参考价值。     

四-对磺酸基-苯基卟啉铁(Ⅲ)的轴向配位快速反应动力学研究

用UnionGikenRA-410温度跃变紫外可见分光光度计研究了二聚的四-对磺酸基-苯基卟啉铁[Fe(Ⅲ)TPPS₄)_D]与咪唑(Im)、2-甲基咪唑(MeIm)、2-乙基-4-甲基咪唑(EMIm)轴向配位快速反应动力学。提出了反应机理,研究了轴向配体和温度对反应的影响,应用Gauss-Newton-Marquardt方法求得基元反应的速率常数及活化参数。     

新型含氮杂环硼-二吡咯亚甲基染料类荧光化合物的合成

以对羟基苯甲醛和2,4-二甲基吡咯为原料,设计并合成了两个新型的8-位苯系取代的硼-二吡咯亚甲基染料类荧光化合物--4,4-二氟-8-[4′-(3-吗啉丙氧基)苯基]-1,3,5,7-四甲基-4-硼-3a,4a-二氮杂-s-引达省和1,4-二{4,4-二氟-8-[4′-(2-乙氧基)苯基]-1,3,5,7-四甲基-4-...     

二茂铁基功能化的氮杂环卡宾银配合物的合成及催化活性

通过N-二茂铁基甲基-N-吡啶基甲基咪唑盐与氧化银在相转移催化条件下反应, 合成了4个二茂铁基功能化的氮杂环卡宾银配合物(NHC)₂AgX(X=PF₆或BF₄), 并利用NMR及X-射线单晶衍射对其结构进行了表征. 在这4个化合物中, 银为二配位结构, 吡啶氮原子并未参与配位. 催化活性测试结果表明, 合成的4个化合物具有高的催化炔、 醛和胺三组分偶联反应活性.     

溶致变色法测定类杂芪染料分子-阶超极化率

Using solvatochromic method the determination of the molecular first-order hyperpolarizabilities of three novel stilbazolium-like dyes and twoknown stilbazolium-like dyes: trans-(pyrrol-2yl) -4-(N-methyl-pyridinio) -stilbazolium iodide(PPSI), trans-(furan-2-yl) -4-(N-methyl - pyridinio)-stilbazolium iodide (FPSI), trans-(thiophene-2-yl) -4- (N-methyl-pyridinio)-stilbazolium iodide (TPSI) and trans-(N-methylpyrrol-2-yl) 4-(N-methyl-pyridinio)-stilbazolium iodide (MPPSI), trans(4-N, N-dimethylamino) -(4- N-methylpwidinio) -stilbazolium iodide(DAPSI) in 8 solvents is presented, and their molecular hyperpolarizabilities are as high as 10-26 -10-27 esu. We have proved that the molecular hyperpolarizabilities is in linear correlation with the electron excessivities of donors for PPSI,FPSI and TPSI in each solvent, this relation give us a way to design molecules that have larger hyperpolallzabilities. Furthermore, our experiments show that the molecules of the five stilbazolium-like dyes have...更多 a larger dipolemoment, when they are in ground state than in excited state.     

2-单核和双核茂铁基-1,3-二烷基苯并咪唑盐的合成、结构及性质研究

以2-二茂铁基苯并咪唑(2)为原料,合成了1-甲基-2-二茂铁基-3-乙基苯并咪唑碘盐(4)和六氟磷酸盐(5);甲酰化的2,2-双二茂铁基丙烷(6)与邻苯二胺在甲醇作溶剂,回流,碘催化下反应,得到2-[1’-(2-二茂铁基丙烷-2-基)二茂铁-1-基]苯并咪唑(7),以7为原料合成了1-甲基-2-[1’-(2-二茂铁基丙烷-2-基)二茂铁-1-基]-3-乙基苯并咪唑碘盐(9)和六氟磷酸盐(10).电化学分析表明所得的盐化合物中,与苯并咪唑阳离子直接相连的二茂铁的氧化电位相对2和7均产生了较大正移.对化合物4的单晶结构进行了解析,晶体结构中存在π-π堆积.UV-Vis吸收光谱表明所得盐化合物具有光致电荷迁移现象.DSC-TG(差示扫描量热-热重)测试表明碘盐4对高氯酸铵(AP)热分解有较好催化效果.     

双二茂铁基吡咯衍生物电荷交互通道

以二茂铁炔烃为原料通过“一锅法”环加成反应合成了一系列2,5-双二茂铁基-1-苯基-吡咯衍生物, 包括: 2,5-双二茂铁基-1-(3-三氟甲基苯基)-吡咯(1), 2,5-双二茂铁基-1-(4-氟苯基)-吡咯(2), 2,5-双二茂铁基-1-苯基-吡咯(3), 2,5-双二茂铁基-1-(4-乙基苯基)-吡咯(4)和2,5-双二茂铁基-1-(4-乙氧基苯基)-吡咯(5), 使用元素分析, 傅里叶变换红外(FTIR)光谱, 质谱(MS)和核磁共振(NMR)等手段对化合物进行了结构表征. 采用循环伏安法(CV), 密度泛函理论(DFT)模拟计算研究了苯基上取代基对双二茂铁间电荷交互的影响. 研究发现第一氧化电位(E_a1), 峰电位差(ΔE)与取代基的哈米特常数(σ), 吡咯¹H NMR的化学位移(δ), 吡咯N原子自然轨道(NBO)电荷之间存在显著线性关联; 同时发现, N原子电荷密度升高, 双二茂铁间电荷交互能力减弱, N原子电荷密度降低, 双二茂铁间电荷交互能力提高. 因此这类双二茂铁基吡咯衍生物中N原子电荷密度对双二茂铁间电荷交互起着关键的影响作用.     

Synthesis of 7-azabicyclo[2.2.1]heptane and 2-oxa-4-azabicyclo[3.3.1]non-3-ene derivatives by base-promoted heterocyclization of alkyl N-(cis(trans)-3,trans(cis)-4-dibromocyclohex-1-yl)carbamates and N-(cis(trans)-3,trans(cis)-4-dibromocyclohex-1-yl)-2,2,2-trifluoroacetamides

We have studied the base-promoted heterocyclization of alkyl N-(cis(trans)-3,trans(cis)-4-dibromocyclohex-1-yl)carbamates and N-(cis(trans)-3,trans(cis)-4-dibromocyclohex-1-yl)-2,2,2-trifluoroacetamides, investigating the effect of the nitrogen protecting group and the relative configuration of the leaving group at C3 and C4 on the outcome of this reaction. We have observed that the sodium hydride-promoted heterocyclization of alkyl N-(cis-3,trans-4-dibromocyclohex-1-yl)carbamates (10, 12, 14, 16, 18) is a convenient method for the synthesis of 7-azabicyclo[2.2.1]heptane derivatives. For instance, the reaction of tert-butyl N-(cis-3,trans-4-dibromocyclohex-1-yl)carbamate (10) with sodium hydride in DMF at room temperature provides 2-bromo-7-[(tert-butoxy)carbonyl]-7-azabicyclo[2.2.1]heptane (2) (52% yield), whose t-BuOK-promoted hydrogen bromide elimination affords 7-[(tert-butoxy)carbonyl]-7-azabicyclo[2.2.1]hept-2-ene (31) in 78% yield, an intermediate in the total synthesis of epibatidine (1). However, the NaH/DMF-mediated heterocyclization of alkyl N-(trans-3,cis-4-dibromocyclohex-1-yl)carbamates (11, 13) is a more structure dependent reaction, where the nucleophilic attack of the oxygen atom of the protecting group controls the outcome of the reaction, giving rise to benzooxazolone and 2-oxa-4-azabicyclo[3.3.1]non-3-ene derivatives, respectively, from low to moderate yields, in complex reaction mixtures. Conversely, the NaH/DMF heterocyclizations of N-(cis-3,trans-4-dibromocyclohex-1-yl)-2,2,2-trifluoroacetamide (40) or N-(trans-3,cis-4-dibromocyclohex-1-yl)-2,2,2-trifluoroacetamide (42) are very clean reactions giving 7-azabicyclo[2.2.1]heptane or 2-oxa-4-azabicyclo[3.3.1]non-3-ene derivatives, respectively, in good yields. Finally, a mechanistic investigation, based on DFT calculations, has been carried out to rationalize the formation of the different adducts.     

三元若丹明激光染料荧光寿命研究

利用单光子计数技术测试了新型三元若丹明激光染料在不同溶剂中的荧光寿命、荧光光谱及其寿命的实验数据.实验表明,所研究的三元若丹明染料存在着有效的分子内能量传递过程,这些过程使得激光染料的荧光量子效率及光稳定性明显改善.     

Synthesis and photophysical properties of hyperbranched polyfluorenes containing 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine as the core

A series of new hyperbranched polymers containing a 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core unit and polyfluorene chain arms have been synthesized via Suzuki coupling, and characterized by NMR, IR and GPC. All the polymers exhibit good thermal stability with a high decomposition temperature. By changing the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio the UV-vis absorption and emission spectra can be partially tuned. It has been found that the polymers containing a low ratio of 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine units (P1-P3) have an absorption maximum around 385 nm, localized in the polyfluorene chain, and a shoulder around 425 nm ascribable to a charge transfer state involving the fluorene and the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core. Increasing the molar ratio of the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine unit enhances the charge transfer band which becomes dominant for P4. The LUMO level of these polymers is relatively low due to the electron affinity of the triazine group. The polymers show dual emission, with a structured band in the blue (410-440 nm), attributed to the polyfluorene, and a broad band in the red (470-500 nm) associated with the charge transfer state. All the polymers exhibit two-photon absorption activity in the range of 660 to 900 nm with the maximum two-photon absorption (TPA) cross-section red-shifted from the corresponding linear absorption. The values of the TPA cross-sections vary from 1000 to 5000 GM, following the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio.     

Structural and photophysical studies of triphenylamine-based nonlinear optical dyes: effects of π-linker moieties on the D-π-A structure

In this work, a series of eight metal-free organic dyes based on triphenylamine as a donor and cyanoacetic acid as an acceptor of electrons with the donor-π-acceptor structure were studied by DFT and TD-DFT methods. Their electronic properties, absorption spectra, and molecular nonlinear optical (NLO) responses have been analyzed and reported. The influence of the change of π-conjugated linker on the electrochemical and photophysical properties of these metal-free organic dyes has been investigated and discussed in detail. The energy gap decreases by going from L1 to L8, which causes a large NLO response for the studied dyes. The natural bond orbital (NBO) analysis reveals that the separation of charge occurred upon photoexcitation and the electrons moved from the donor to the acceptor moiety. A high NLO response reveals that this kind of metal-free organic dyes has eye-catching and remarkably large first hyperpolarizability β_tot values, especially for L7 ((E)-2-cyano-3-(3-((E)-2-(3-((E)-4-(diphenylamino)styryl)benzo[c]thiophen-1-yl)vinyl)benzo [c]thiophen-1-yl)acrylic acid) and L8 ((E)-2-cyano-3-(7-((E)-2-(7-((E)-4-(diphenylamino)styryl)thieno[3,4-b]pyrazin-5-yl)vinyl)thieno[3,4-b]pyrazin-5-yl)acrylic acid) with 150423.50 (a.u) and 202773.63 (a.u), respectively. Our research has been carried out to extend the conjugation of organic materials by controlling their π-conjugated linker to design new appealing NLO compounds. This study shows that these dyes are promising and have special properties for modern hi-tech applications such as solar cells, transistors, and organic light-emitting diodes (OLEDs), and even these properties can be adjusted and enhanced by the incorporation of the benzothiophene or thienopyrazine derivatives as a bridge so as to improve from L7 to L8.     

Structural and environmental requirements for quenching of singlet oxygen by cyanine dyes

Singlet-oxygen quenching constants were measured for 19 cyanine dyes in acetonitrile. The most efficient quenchers were 1-butyl-2-[2-[3-[(1-butyl-6-chlorobenz-[cd]indol-2(1H)- ylidene)ethylidene]-2-chloro-1-cyclohexen-1-yl]ethenyl]-6-chlorobenz[cd] indolium and 6-chloro-2-[2-[3-(6-chloro-1-ethylbenz[cd]indol-2(1H)-ylidene) ethylidene]-2-phenyl-1-cyclopenten-1-yl]ethenyl]-1-ethyl-benz[cd]indolium, having quenching constants with diffusion-controlled values of 2.0 +/- 0.1 x 10(10) and 1.5 +/- 0.1 x 10(10) M-1 s-1, respectively. There was a trend toward increased quenching constants for cyanine dyes with the absorption band maxima at longer wavelengths. However, the quenching constants correlated better with the oxidation potentials of the cyanine dyes, suggesting that quenching proceeds by charge transfer rather than energy transfer. The quenching constants for 1,1',3,3,3',3'-hexamethylindotricarbocyanine perchlorate and 1,1'-diethyl-4,4'-carbocyanine iodide were measured in several solvents as well as in aqueous solutions of detergent micelles. In different solvents, the quenching constants varied by as much as a factor of 50. The quenching constants were largest in solvents with the highest values on the pi* scale of Kamlet, Abboud, Abraham and Taft. This was consistent with quenching occurring by charge transfer. Within cells, cyanine dyes concentrate in membrane-bound organelles. The quenching constants were substantial within detergent micelles. To the extent that micelles are models for biological membranes, cyanine dyes may be effective biological singlet-oxygen quenchers.