TiO2纳米晶电极上半菁衍生物分子设计中空间位阻效应的研究

设计合成了具有不同空间位阻的吡啶盐类和喹啉盐类半菁染料 (E) N ( 4 磺酸根丙基 ) 4 [2 ( 4 N ,N 二乙基氨基苯基 )乙烯基 ]吡啶盐 (EPS) ,(E) N ( 4 磺酸根丁基 ) 4 [2 ( 4 N ,N 二乙基氨基苯基 )乙烯基 ]吡啶盐 (EPS4)和 (E) N ( 4 磺酸根丁基 ) 4 [2 ( 4 N ,N 二乙基氨基苯基 )乙烯基 ]喹啉盐 (EQS4) ,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中 .研究发现 :对于吡啶类半菁染料而言 ,无论是以三个亚甲基或是以四个亚甲基来连接吸附基团RSO-3 和发色团时 ,单个的EPS和EPS4分子的光电响应行为一致 .但是由于以三个亚甲基来连接时 ,与EPS4相比 ,染料EPS的空间位阻相对较小 ,有利于其在多孔膜上的吸附 ,最终结果是染料EPS对TiO2 纳米晶电极的敏化作用好于EPS4.以喹啉环为受电子基团的染料EQS4与同样含有四个亚甲基的以吡啶环为受电子基团的EPS4相比 ,单个EQS4分子的光电响应行为虽然好于EPS4分子 ,但由于EQS4分子间的空间位阻较大 ,影响了它在多孔电极上的吸附 ,致使其敏化的太阳能电池的总光电转换效率有所下降     

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.     

N-甲基丙烯酰-N′-嘧啶基哌嗪及其聚合物敏化的丙烯腈光聚合

我们曾报道过同一分子中含有给电子生色基团和电子受体基团的一类功能性单体,如甲基丙烯酸-4-N,N-二甲氨基苄酯(DMABMA),N-(4-N′,N′-二甲氨基苯基代丙烯酰胺,N-(4-N′、N′)-二甲氨基苯基代甲基丙烯酰胺(DMAPMA),8-丙烯酰氧喹啉(AQ),N-丙烯酰-N′-苯基哌嗪(APP)的合成、聚合以及单独或与过氧化二酰构成氧化还原体系以引发烯类单体的聚合研究。N-甲基丙烯酰-N′-嘧啶基哌嗪(MPMP)     

新型半菁染料阳离子和含锌硫代富瓦烯配阴离子的电荷转移复合物光电响应性质的研究

对一种新型半菁发色基团的碘化物--(反式)-N-十八烷基-4-(2-(4-(2-二甲基氨基)苯基)乙烯基)喹啉碘化物和含锌硫代富瓦烯配阴离子形成的电荷转移复合物:二-[(反式)-N-十八烷基-4-(2-(4-(2-二甲基氨基)苯基)乙烯基)喹啉]合硫代富瓦烯锌酸盐的成膜性以及它们的LB膜修饰ITO电极上的光电响应性质进行比较研究,用含锌硫代富瓦烯配阴离子对这种半菁发色团阳离子进行组装后,能够改善其成膜性,使单位面积上的半菁发色团数目增加.同时,含锌硫代富瓦烯配阴离子的强吸电子能力还影响半菁发色团的电荷分布,使之有利于电荷分离,从而提高了光电流的量子产率.在无外界影响时,其光电转化的量子产率达0.9%,是碘化物的1.8倍.     

敏化染料分子长径比对太阳能电池性能的影响

采用同一系列但分子长径比不同的3种染料:2-氰基-3-[2-[4-{2-[4-N,N-二(4-甲基苯基)氨基苯基]乙烯基}-苯基氨基)-嘧啶-5-取代基]-丙烯酸(MTPA-Pyc)、2-氰基-3-(4-{2-[4-N,N-二(4-甲基苯基)氨基苯基]乙烯基}-苯基)-丙烯酸(MTPAcc)和2-氰基-3-[4-N,N-二(4-甲基苯基)氨基苯基]-丙烯酸(MTPAc),研究了在不同吸附溶剂中3种染料分子在Ti O2上的吸附量和聚集态,探讨了敏化染料分子长径比对染料敏化太阳电池性能的影响.结果表明,MTPAcc具有最合适的分子长径比,其在Ti O2表面的吸附量及应用的光电性能最高;吸附溶剂的极性增大有利于提高染料的吸附量,但也会影响染料分子的聚集态.当以四氢呋喃为吸附溶剂时,MTPAcc在Ti O2表面的吸附量大且不发生聚集,对应的敏化太阳能电池器件在所有结果中表现最好,在490 nm处的单色光光电转化效率(IPCE)极值达到84%,总光电转化效率(η)达到5.72%.     

N-(2-乙烯氧乙基)-1,8-萘二甲酰亚胺聚合物与共聚物的荧光行为

<正> 我们曾报道过一系列含有给电子生色基团的丙烯酰类单体如甲基丙烯酸二甲氨基苄酯、N-(N′,N′-二甲氨基苯基)丙烯酰胺类、8-丙烯酰氧喹啉类、N-丙烯酰-N′-苯基哌嗪类、N-丙烯酰-N′-嘧啶哌嗪类、N-甲基丙烯酰氧乙基-N-甲基代苯胺等的合成、聚合、引发行为以及它们的聚合物的荧光行为。这些单体结构的共同点在于其双键为缺电子性而生色基团为给电子性,因而在荧光行为上,由于生成激基复合物或电荷转移而发生荧光     

半菁类染料敏化太阳能电池的光电化学性能研究

研究了三种不同长度碳链取代的半菁类染料2-[4-(N,N-二羧乙基)氨基]苯乙烯基-1,3,3-三甲基苯并吲哚鎓碘(BIDC1)、2-[4-(N,N-二羧乙基)氨基]苯乙烯基-1-丁基-3,3-二甲基苯并吲哚鎓碘(BIDC2)和2-[4-(N,N-二羧乙基)氨基]苯乙烯基-1-辛基-3,3-二甲基苯并吲哚鎓碘(BIDC3)敏化太阳能电池的光电化学性能。其中BIDC1的敏化效果最好,在100mW/cm2氙灯光源下,开路电压、短路电流、填充因子和转换效率分别是430mV、1.31mA/cm2、0.52、0.29%。研究表明,随着半菁染料碳链取代基的增长,光电转换效率逐渐降低。     

N-甲基-N-(2-甲基丙烯酰氧乙基)苯胺敏化的丙烯腈光聚合

含有芳香叔胺基的烯类单体如N,N-二甲氨基苯乙烯,N-4-N',N'-二甲氨基苯基代丙烯酰胺(DMAPAA),N-4-N',N'-二甲氨基苯基代甲基丙烯酰胺(DMAPMA),甲基丙烯酸-4-N,N-二甲氨基苄酯(DMABMA),8-丙烯酰氧喹啉(AQ)等不仅与过氧化物构成氧化还原引发体系以引发其它烯类单体的光聚合还可以作为光敏剂引发烯类单体的光聚合。由于这类功能性单体在同一分子中既含有缺电子双键基团又含有供电子生     

8-丙烯酰氧喹啉及其聚合物增感的丙烯腈光聚合

<正> 我们曾研究过电子给体基团和电子受体基团共存于同一分子中的一类功能性单体,如甲基丙烯酸-4-(N,N)-二甲氨基苄酯(DMABMA)、N-(4-N′,N′-二甲氨基苄基)丙烯酰胺(DMAPAA)、8-丙烯酰氧喹啉(AQ)。N-丙烯酸-N′=苯基哌嗪(APP)等     

吡唑啉衍生物与溶剂相互作用的研究

通过对一类吡唑啉衍生物（1-苯基-3-（N，N-二甲基氨基苯乙烯）-5-（4-N，N-二甲基氨基苯基）-2-吡唑啉）在不同溶剂中的光谱行为，研究了该衍生物和溶剂分子间的一般相互作用和特殊相互作用．发现利用吡唑啉溶液的荧光猝灭现象能对其和溶剂分子间不同相互作用问题提供有价值的信息．     

Enhancement of Photocurrent Generation of a Novel Stilbazolium Dye Dimer in LB Monolayer Films

A novel dye dimer,bis-{[1-(N-hexadecyl-4-pyridinium)-2-(4-N,N-dimethylaminopheyl)] ethenyl} methane diiodide (C16BP) was synthesized,and the photoelectrochemistry of the dye Langmuir-Blodgett monolayer modified ITO electrode was investigated.For comparison,the photoelectrochemistry of the monomer (E)-N-hexadexyl-4-[2-(4-N,N-dimethylaminophenyl) ethenyl] pyridinium iodide (C16P) was also measured.The results show that the photocurrent generation property of the dimer is enhanced.The photocurrent generation quantum yield is 0.38% for C16BP,while that for C16P is 0.23%.     

Hexasubstituted donor-acceptor benzenes as nonlinear optically active molecules with multiple charge-transfer transitions

The synthesis of three novel nonlinear optical (NLO) chromophores with threefold symmetry, namely 1,3,5-tris(4-N,N-diethylaminophenyl)-2,4,6-tris(4-nitrophenyl)benzene (3), 1,3,5-tris(4-N,N-dihexylaminophenylbutadiynyl)-2,4,6-tris(4-nitrophenyl)benzene (13) and 1,3,5-tris(4-N,N-dihexylaminophenylethynyl)-2,4,6-tris(4-nitrophenylethynyl)benzene (4 b), is reported. We used the [Co(2)(CO)(8)]-catalysed trimerisation of 4-N,N-diethylamino-4'-nitrotolane (5) to prepare 3. The trimerisation experiment carried out with 1-(4-N,N-diethylaminophenyl)-6-(4-N,N-nitrophenyl)hexatriyne (6) and [Rh(PPh(3))(3)Cl] afforded 13. A stepwise approach was used to prepare 4 b. 1,3,5-Trichloro-2,4,6-triiodobenzene (8 b) was coupled with 4-nitrophenyl-acetylene (14) under Pd(0) catalysis to yield 1,3,5-trichloro-2,4,6-tris(4-nitrophenylethynyl)benzene (15). The coupling reaction of 15 with 4-N,N-dihexylaminophenylethynyltributylstannane (21) led to 4 b. X-ray investigations on 3, 4 b and 13 confirmed the structural assignments and revealed that the peripheral aryl rings in 4 b are less twisted around the connecting bonds than in 3 and 13. A large second-order polarisability (beta) of 4 b relative to 3 and 13 was determined by hyper-Rayleigh scattering (HRS). Compound 4 b represents an NLO chromophore with second-order polarisabily among the highest obtained so far for two-dimensional nondipolar NLO chromophores.     

Development of a quinoxaline-based fluorescent probe for quantitative estimation of protein binding site polarity

The compound 2-[(1E)-2-(1H-pyrrol-2-yl)ethenyl]-quinoxaline (PQX) is a promising fluorescent chromophore for the estimation of protein binding site polarity, due to its full-color solvatochromic fluorescence. A linear relationship was obtained between the peak emission wavenumber and E(T)(N) (normalized solvent polarity). The BSA binding site polarity was estimated from the solvatochromic plot.     

Syntheses, spectroscopic and molecular quadratic nonlinear optical properties of dipolar ruthenium(II) complexes of the ligand 1,2-phenylenebis(dimethylarsine)

Six new complex salts trans-[Ru(II)Cl(pdma)2L][PF6]n [pdma = 1,2-phenylenebis(dimethylarsine); L = (E,E,E)-1,6-bis(4-pyridyl)hexa-1,3,5-triene (bph), n= 1, 5; L =N-methyl-4-[(E)-2-(4-pyridyl)ethenyl]pyridinium (Mebpe+), n= 2, 7; L =N-methyl-4-[(E,E)-4-(4-pyridyl)buta-1,3-dienyl]pyridinium (Mebpb+), n= 2, 8; L =N-methyl-4-[(E,E,E)-6-(4-pyridyl)hexa-1,3,5-trienyl]pyridinium (Mebph+), n= 2, 9; L = bis(4-pyridyl)acetylene (bpa), n= 1, 10; L =N-methyl-4-[2-(4-pyridyl)ethynyl]pyridinium (Mebpa+), n= 2, 11] have been prepared. The electronic absorption spectra of 5 and 7-11 display intense, visible metal-to-ligand charge-transfer (MLCT) bands, with lambdamax values in the range 434-492 nm in acetonitrile. Cyclic voltammetric studies reveal reversible Ru(III/II) waves with E(1/2) values in the range 1.06-1.15 V vs. Ag-AgCl, together with irreversible L-based reduction processes. Along with a number of previously reported related compounds (B. J. Coe et al., J. Chem. Soc., Dalton Trans., 1996, 3917; 1997, 591; 2000, 797), salts 5 and 7-11 have been investigated by using Stark (electroabsorption) spectroscopy in butyronitrile glasses at 77 K. These studies have afforded dipole moment changes Deltamu12 for the MLCT transitions which have been used to calculate molecular static first hyperpolarizabilities beta0 according to the two-state equation beta0= 3Deltamu12(mu12)2/(Emax)2 (mu12 = transition dipole moment, Emax = MLCT energy). MLCT absorption and electrochemical data show that a trans-[Ru(II)Cl(pdma)2]+ centre is considerably less electron-rich than a [Ru(II)(NH3)5]2+ unit. Although the beta0 responses of the pdma complexes are only a little smaller than those of their [Ru(II)(NH3)5]2+ analogues, this result is partly attributable to unexpected changes in the relative mu12 values on freezing. Thus, substantial increases in mu12 for the arsine compounds act to partially offset the beta0-decreasing influence of their higher Emax values when compared with the analogous pentaammine species. Single crystal X-ray structures have been obtained for the salts 1(.)2.5MeCN, 4(.)2MeCN, 7 and 11, but only 1(.)2.5MeCN adopts a non-centrosymmetric space group (Fdd2) such as may show bulk NLO effects.     

A swift dye uptake procedure for dye sensitized solar cells

Solar cells based on swift self-assembled sensitizer bis(tetrabutylammonium)-cis-di(thiocyanato)-N,N'-bis(4-carboxylato-4'-carboxylic acid-2,2'-bipyridine)ruthenium(II) (N719) on double layers of 12 + 4 microm thick nanocrystalline TiO2 films exhibit the incident monochromatic photon-to-current conversion efficiency (IPCE) 90% and show a short circuit current density of 17 mA cm(-2), 750 mV open circuit potential and 0.72 fill factor yielding power conversion efficiencies over 9.18% under AM 1.5 sun. For the first time highest power conversion efficiencies are obtained for dye sensitized solar cells using a swift self-assembled procedure.     

Synthesis of New Near-infrared Fluorescent Dyes

Inrecentyears,agrowingnumberofscientistsareIookingforpr0cedurestolabelbiologicallyimp0rtantmolecules(suchasDNA,Proteins,etc.)'-'.Oneefficientwaycurrentlyexploitedistheuseofnear-infraredfluorescentdyesasfluorogeniclabels.AIthoughtherearemanyfluorescentdyescommerciallyavailable,onlyseveralclassesofm0lecuIescanbe0peratedinthefar-visibleornear-infraredregion(6O0-lO00nm)whicharetheareas0flowinterference.Inanattemptt0lookfornewnear-infraredfluorescentmolecules,0urgroupsynthesizedaseriesofbenzo[a…     

新型含噻吩基8-羟基喹啉锌配合物的合成及光电性能简

设计合成了含噻吩基的新型配体(E)-2-[2-(3-噻吩基)乙烯基]-8-羟基喹啉(4)及相应的锌配合物5,产物结构经核磁共振、红外光谱和元素分析进行表征. 利用X射线单晶衍射仪测定了中间体(E)-2-[2-(3-噻吩基)乙烯基]-8-乙酰氧基喹啉(3)和配体4的单晶结构,结果表明中间体3晶体分子间并无明显的氢键作用,分子间呈交错堆叠;配体4分子之间由硫氢氧键弱作用相互排列形成网状结构. 通过核磁滴定及紫外和荧光滴定模拟了配体4在溶液中与金属锌的配位过程. 固体荧光寿命研究结果表明,配合物5的荧光寿命为18.8 ms. 通过电致发光器件研究发现,配合物5作为发光层具有良好的电致发光性能,同时具有较好的电子传输能力.     

Surface interaction and self-assembly of cyclodextrins with organic dyes

The interaction of seven novel substituted merocyanine dyes, i.e. 1-methyl-4-[2-(3-methoxy-4-hydroxyphenyl)ethenyl)]pyridinium iodide, 1-methyl-4-[2-(3,5-dimethoxy-4-hydroxyphenyl)ethenyl)]pyridinium iodide, 1-methyl-4-[2-(4-dimethylaminophenyl)ethenyl)]pyridinium iodide, their quinoide forms as well as 1-methyl-4-[2-(3-methoxy-4-oxocyclohexadienilydene)ethylidene]-1,4-dihydropyridine, 1-methyl-4-[2-(3,5-dimethoxy-4-oxocyclohexadienilydene)ethylidene]-1,4-dihydropyridine, with α-CD, γ-CD as well as functionalized γ-cyclodextrin phosphate sodium salt is studied by the methods such as UV–Vis and fluorescence spectroscopy, linear-polarized infrared (IR-LD) spectroscopy of oriented colloids in nematic host, ¹H- and ¹³C-NMR spectroscopy, HPLC ESI tandem mass spectrometry, scanning electron and tunneling microscopy, powder X-ray diffraction as well as thermal methods. A formation of the 1D and 2D “supramolecular polymers” with nanosizes is found. The dyes are adsorbed on the CDs surface and form a hexagonal microcrystalline sub-structures. Remarkable fluorescence properties depending of the type of the substituent in the dyes, in solid-state are observed.