2-十八烷基-7,7,8,8-四氰基对醌二甲烷和3,3′,5,5′-四甲基联苯胺电荷转移配合物LB膜的制备和表征

利用LB技术制备了2-十八烷基-7,7,8,8-四氰基对醌二甲烷(C18TCNQ)和3,3,′5,5′-四甲基联苯胺(TMB)的电荷转移配合物(CT comp lex)薄膜,即TMB.C18TCNQ LB膜.利用红外(IR)光谱、紫外-可见-近红外(UV-V is-NIR)光谱以及原子力显微镜(AFM)研究了TMB.C18TCNQ在LB膜中的分子取向、结构及表面形貌.结果表明,配合物为混合堆积类型,LB膜中电子给体TMB和电子受体C18TCNQ的环面分别垂直于固体基板表面,而且给体和受体以面对面的方式堆积.5层TMB.C18TCNQ LB膜的AFM照片显示,其表面形貌是由许多堆积在一起的六边形片状微晶组成的,微晶的宽度约为180 nm.与通过LB技术和掺杂技术制备的TMB.C18TCNQ掺杂膜比较,TMB.C18TCNQ LB膜具有明显不同的结构,其长的脂肪烃链有向垂直于基板表面方向变化的趋势,LB膜与掺杂膜的表面形貌也有明显不同.这表明不同的制备方法可以影响薄膜的结构和形貌.     

非两亲性四硫代富瓦烯导电LB膜的研究

近年来，利用LB技术制备电活性的有机超薄膜受到广泛的关注．导电LB膜的膜材料主要是含有受体化合物7，7’，8，8’-四氰基二亚甲基苯醌（TCNQ）的电荷转移复合物[1~3]以及给体分子[4，5]，特别是四硫代富瓦烯（TTF）衍生物[6~8]．尽管LB膜多由带长链的两亲性分子组装而成，但是对非两亲性TTF衍生物LB膜的研究[9~11]结果表明，引入长链烷基并非制备TTF类电荷转移复合物LB膜的先决条件．该结果极大地拓展了LB膜材料的研究范围．本文报道非两亲性TTF衍生物与花生酸混合导电LB膜的制备、结构表征与导电性能研究．1实验部分利用亚磷…     

Ag(TCNQ)准一维微米结构的制备及表征

利用溶液化学反应法制备了准一维结构的金属有机配合物Ag(TCNQ). X射线衍射(XRD)表明，所制备的Ag(TCNQ)为晶态结构;扫描电子显微镜(SEM)的观察证明，Ag(TCNQ)为准一维的微米管或线；Raman 测试结果表明，单根的Ag(TCNQ)形成时,Ag原子与TCNQ分子之间发生了电荷转移.对样品的制备工艺,即 Ag膜厚度和浸入溶液的反应时间对生成Ag(TCNQ)晶体形貌的影响进行了研究.结果表明，Ag膜越薄，生长出的晶体越稀疏;Ag膜与TCNQ乙腈溶液的反应时间影响其形貌的变化.反应历经三个阶段,晶体形成和长大阶段、反应完全阶段及溶解阶段.     

四硫代富瓦烯及其CT复合物导电LB膜

通过Langmuir-Blodgett（LB）技术制备导电性有机超薄膜近年来受到了广泛的关注，导电LB膜的膜材料主要是含有电子受体77’，8，8’一四氨基二亚甲基本自（TCN则的电行转移（CT）复合物间以及给体分子特别是四流代宫瓦烯衍生物［‘刮.在以前的工作中，我们曾报导了四等基硫四硫     

基于四硫富瓦烯衍生物Langmuir-Blodgett膜的研究进展

在简要介绍了Langmuir-Blodgett (LB)膜的基础上, 主要依据制备LB膜的四硫富瓦烯(TTF)衍生物化学结构的不同, 概括了基于两亲性TTF衍生物、非两亲性TTF衍生物、TTF电荷转移(CT)复合物或盐、以及TTF金属络合物LB膜的制备、结构表征与性能研究进展. 介绍了基于TTF衍生物的LB膜在导电、化学及生物传感器、光学以及磁性方面的应用, 并对基于TTF衍生物LB膜的发展进行了展望.     

聚酰亚胺LB膜热解制备SiC薄膜的XPS研究

用XPS对沉积在硅基片上的聚酰亚胺LB膜以及由它真空热解制备的SiC薄膜进行了研究 ,并对其形成过程进行了跟踪分析 .XPS结果显示聚酰亚胺LB膜结构均匀 ,质量良好 ;真空热解时 ,约在 6 70℃时LB膜中的C与衬底Si反应形成SiC ;Ar离子溅射深度俄歇谱表明所制备的SiC膜中Si和C浓度成梯度分布 ,说明SiC是由Si和C相互扩散反应形成的     

TC16PyP(4)/AnQ混合LB膜结构的研究

我们曾报道了沉积在 Sn O2 导电玻璃基片上的 5 ,1 0 ,1 5 ,2 0 -四 -(4 -十六烷基吡啶基 )卟啉 [TC16 Py P(4 ) ]LB膜的光电性质 [1] .结果表明 ,电解质溶液中含有电子给体和受体时 ,由于超敏化作用 ,样品光电效应明显增强 .在研究其它 LB膜时 ,我们发现将两亲性卟啉分子 A与等物质的量憎水性化合物 B一起拉膜时 ,有可能得到一一对应的混合 LB膜[2 ] .如果 A和 B分别为电子给体和受体 (反之亦然 ) ,A和 B之间应有较强的相互作用 .将这种混合 LB膜沉积在基板上 ,可能表现出新的电子与光学性质 ,从而得到具有多种功能的新材料 .本文…     

藻胆蛋白的Langmuir-Blodgett膜——Ⅱ.R-藻红蛋白的光电化学性质研究

通过由R-藻红蛋白(R-PE)LB膜组成的光电池,研究了R-PE的电荷转移现象及光电化学行为.实验表明,由R-PE LB膜组成的光电池能产生光生电流,且当电解质溶液中存在电子给体和受体时光电流明显增大,说明R-PE光生电流的产生是由电荷转移引起的.进一步的对比实验说明,其光生电流是来源于蛋白所含发色团的光诱导电荷分离性质;光电流作用光谱也进一步证实了上述观点.当电解质溶液中存在或不存在电子给体时,光电流方向总是流向饱和甘汞电极(SCE),说明电子是从R-PE注入SnO_2光学透明电极(SnO_2 OTE)的导带;当电解质液中存在电子受体时,光电流方向总是流向SnO_2 OTE,说明这时电子是从SnO_2电极的导带注入R-PE分子.据此提出了R-PE光诱导电荷转移的机制.经测定由R-PE LB膜组成的光电池的光电转换量子效率Ф_(520MM)=3.4%,光生电势达400mV,且具有很好的光学稳定性,这说明R-PE是优良的生物光电转换功能材料.实验中,还测定了电解质溶液pH值,电子给体浓度,蛋白LB膜层数及光照时间对R-PE光电流的影响.     

新型钒取代杂多酸电荷转移盐的合成和表征

以不同钒取代的Danson结构的杂多磷钼酸为电子受体 ,N ,N 二甲苯胺为电子给体合成了两种新型电荷转移盐配合物 8C8H11N·H8P2 Mo16V2 O62 ·3C3 H7NO·5H2 O和 8C8H11N·H10 P2 Mo14 V4O62 ·4C3 H7NO。并用元素分析、红外光谱、固体漫反射电子光谱等进行了表征。结果表明 :有机电子给体与杂多酸阴离子间有强烈的相互作用 ,配合物在光激发下发生分子内的电荷转移 ,导致有机阳离子的氧化和杂多阴离子的还原。ESR测试结果显示 ,杂多阴离子的还原反应处于单电子还原阶段 ,阴离子中VV 还原为VⅣ     

一个对称萘酞菁的LB膜及其二阶非线性光学性质的研究

用水平提拉法制备了四叔丁基萘酞菁锌的LB膜。利用表面压-面积曲线、紫外-可见吸收光谱、小角X-射线衍射等表征了LB膜的结构,结果表明该化合物可以形成较高质量的具有很好层状结构的多层LB膜,在膜中分子大环平面垂直于基片平面并且以分子平面并不完全重合的H-聚集体存在。采用透射SHG方法测量了相应LB膜的二阶非线性光学性质,结果显示在实验条件下该化合物LB膜的宏观二阶非线性系数以及分子超极化率分别为X     

Studies on the structure and miscibility of mixed Langmuir-Blodgett films of a double-armed dibenzo-18-crown-6 ether with stearic acid

Reported here is the study on the structure of Langmuir-Blodgett (LB) films of double-armed dibenzo-18-crown-6 contain biphenyl (DACE) which are newly synthesized and mixed with stearic acid (SA). In addition, the miscibility of the two compounds was also tested by the measurement of the surface pressure-area (pi-A) isotherms of DACE and DACE/SA with various proportions. It is noted that there is no phase segregation in the mixed monolayer film of DACE/SA. Upon calculation of the excess surface area, it is concluded that the SA molecule can enter into the crown ether ring, while an 18C6 ring can host a maximum of one SA molecule. The difference of spectroscopic properties of DACE in LB films and bulk solution has been investigated by ultraviolet-visible (UV-vis) and Fourier-transfer infrared (FTIR) measurements. Molecules of DACE exist in the mixed LB films as monomers in contrast to those in the concentrated solution as aggregates. The hydrocarbon chains in DACE and DACE/SA LB films are tilted to the normal of the substrate surface, but perpendicular to the dipole moment of CO. Both CO bonds in the phenyl ethers and carboxylic ester of DACE, and the long axes of phenyl rings are aligned nearly perpendicular to the substrate surface. Infrared spectra of mixed LB films of DACE/SA present further evidence that the SA molecules enter into the crown ether rings of DACE.     

Direct fabrication of conductive LB films composed of N-docosylpyridinium-TCNQ

Langmuir-Blodgett (LB) films of N-docosylpyridinium-TCNQ (NDP-TCNQ) were prepared in air. The films deposited at the room temperature showed in-plane conductivity of 4×10-3 S.cm-1 and its absorption spectra in UV and IR regions resembled those for the films composed of mixed-valence TCNQ salts of NDP-(TCNQ)2 rather than for the NDP-TCNQ LB films preparaed under protection of nitrogen. In the case that the films left in a warm environment after each dipping cycle, the absorption in the corresponding region changed. Spectral analysis and XPS study revealed that more TCNQ molecules were produced. The oxidation of TCNQ- in air was considered to be the origin of neutral TCNQ formed.     

Molecular Orientation and Structural Characterization of Ultrathin Films of C12AzoNaph(1,4)C6N-SDS Studied by FT-IR and NIR-SERS Spectroscopies

IntroductionAzobenzene- containing long- chain fatty acidsand their ammonium amphiphiles have recentlyaroused a great interest of some researchersbecause of their promising photochromicproperties[1— 6 ] . In order to understand theinteresting physical properties the LB films withazo chromophores show,a structure- functionrelationship of the films must be explored.Thusfar,infrared spectroscopy has been usedextensively for the investigations of molecularaggregation,orientation and structuralch…     

Tuning the arrangement of mono-crown ether-substituted phthalocyanines in Langmuir-Blodgett films by the length of alkyl chains and the cation in subphase

Amphiphilic phthalocyanines with one crown ether and three alkyl chain substitutions can form stable monolayers on a water surface. This monolayer can be transferred to a substrate by a vertical dipping method. The arrangement of phthalocyanine molecules in LB films was affected by the length of alkyl chains and the coordination of alkali ions in crown ether. Davydov splitting was observed in the absorption spectra of the LB films of phthalocyanine with the shortest alkyl chain substitutions, and this splitting was affected by the alkali ions in the subphase.     

酞菁铜与四氰代二甲基苯醌电荷转移反应的测定

用红外光谱、紫外可见光谱、循环伏安法等研究了三．（２，４－二特戊基苯氧基）－８－喹淋氧基酞菁铜（简称酞菁铜）和２－十八烷基－７，７，８，８－四氰二甲基苯醌（简称Ｃ１８－ＴＣＮＱ）在Ｌａｎｇ－ｍｕｉｒ－Ｂｌｏｄｇｅｔｔ（ＬＢ）膜中的电荷转移。实验结果表明，在交替和混合ＬＢ膜中，酞菁铜和Ｃ１８－ＴＣ－ＮＱ分子之间均发生了电荷转移，其中酞菁铜为给体分子，ＴＣＮＱ为受体分子。在混合ＬＢ膜中，电荷转移程度较大。电导率测量表明荷移反应使ＬＢ膜的电导率较纯酞菁铜ＬＢ膜提高了３个数量级。     

In situ synthesis, photometric and spectroscopic studies of chelating system during the 1,4,7,10,13,16-hexaoxacyclooctadecane charge transfer reaction with different acceptors

Electron donor acceptor complexes (EDA) of the 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6) as a rich donor were spectrophotometrically discussed and synthesized in solid form according the interactions with different nine of usual π-acceptors like 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione (p-chloranil; p-CHL), tetrachloro-1,2-benzoquinone (o-chloranil; o-CHL), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), tetracyanoquinodimethane (TCNQ), 2,6-dichloroquinone-4-chloroimide (DCQ), 2,6-dibromoquinone-4-chloroimide (DBQ), 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (chloranilic acid; CLA), N-bromosuccinimide (NBS), 2,4,6-trinitrophenol (picric acid; PA). Spectroscopic and physical data such as formation constant (K(CT)), molar extinction coefficient (?(CT)), standard free energy (ΔG°), oscillator strength (f), transition dipole moment (μ), resonance energy (R(N)) and ionization potential (I(p)) were estimated in chloroform or methanol at 25°C. Based on the elemental analysis and photometric titrations the CT-complexes were formed indicated the formation of 1:1 charge-transfer complexes for the o-CHL, TCNQ, DCQ, DBQ and NBS acceptors but 1:3 ratio for p-CHL, DDQ, CLA and PA, respectively. The charge-transfer interactions were interpretative according to the formation of dative ion pairs [18C6(?+), A(?-)], where A is acceptor. All of the resulting charge transfer complexes were isolated in amorphous form and the complexes formations on IR and (1)H NMR spectra were discussed.     

不同羧酯比的聚马来酸十八醇酯齐聚物的镉盐LB膜成膜特性研究

由聚马来酸杆和十八醇合成了一系列不同羧酯比的聚马来酸十八醇酯（PMA），并以其为成膜材料、CdCl2水溶液为亚相制备了一系列聚马来酸十八醇酯镉盐（CdPMA）LB膜．借助小角X射线衍射和红外吸收光谱表征了成膜条件及羧酯比对CdPMA膜有序结构的影响．在较高膜压（30mN／m）和快速提拉（10cm／min）条件下，低羧酯比的CdPMA可得到有序性很高的Y-型LB多层膜；高羧酯比的CdPMA得不到高有序性的LB多层膜．     

Spectroscopic and thermal studies on the charge transfer complexes formed between morpholine as donor with p-chloranil and 7,7′,8,8′-tetracyanoquinodimethane

Charge-transfer (CT) complexes formed between morpholine (Morp) as donor with CHL and TCNQ as acceptors have been studied spectrophotometrically. The synthesis and characterization of morpholine CT-complexes of p-chloranil, [(Morp)(CHL)] and 7,7′,8,8′-tetracyanoquinodimethane, [(Morp)(TCNQ)] were described. These complexes are readily prepared from the reaction of Morp with CHL and TCNQ within CHCl₃ and/or MeOH solvents. IR, UV–Vis techniques, elemental (C, H, and N) and thermal analyses (TG/DTG) characterize the two Morp charge-transfer complexes. Benesi–Hildebrand and its modification methods were applied to the determination of association constant (K), and molar extinction coefficient (?).     

In situ spectroscopic characterization of rectifying molecular monolayers self-assembled on gold.

We report visible, Raman, and infrared spectra of self-assembled monolayers (SAMs) formed by the donor-(pi-bridge)-acceptor chromophore, Z-beta-[N-(omega-acetylthioalkyl)-4-quinolinium]-alpha-cyano-4-styryldicyanomethanide (CH3CO-S-CnH2n-Q3CNQ where n=8, 10), on gold-coated substrates. The data are compared with the spectra collected for the same compound in solution and in the solid state, and with those obtained for a Langmuir-Blodgett (LB) monolayer of C16H33-Q3CNQ deposited on gold. Spectral analysis confirms that in solution, in the solid state and in the LB film the chromophore has a zwitterionic (D+-pi-A-) ground state. At variance with this well-known result, our data show that in SAMs deposited on gold the chromophore has a more neutral, quinoid ground state. We relate this difference to the different packing of the molecules in the two different films: in SAMs in fact the chromophores stand almost vertical with respect to the substrate, whereas in LB films they make an angle of about 45 degrees. The Q3CNQ molecule is a well-known molecular rectifier, and for SAMs we were able to check the direction of electron flow at forward bias on the same samples that have been characterized spectroscopically, shedding light on the rectification mechanism.     

两种表征金属有机双层膜络合和金属薄膜氧化反应动力学的方法

建立了两种新的薄膜反应动力学表征方法, 即透射光谱法和方块电阻法, 以克服传统动力学表征手段在薄膜体系氧化与络合反应过程中应用的局限性. 以透射光谱为表征手段, 得到了Ag/TCNQ(四氰基对醌二甲烷)金属有机双层薄膜的络合反应动力学曲线; 以方块电阻为表征手段, 得到了Cu薄膜的氧化反应动力学过程.