酞菁铜与四氰化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（２，４－二特戊苯氧基）－８－喹啉氧基酞菁铜和２－十八烷基－７，７，８，８－四氰二基苯醌在Ｌａｎｇｍｕｉｒ－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，电葆转移程度较大。电导率测量表明荷移反应使ＬＢ膜的电导率较     

双（1,2—丙二胺）合铜的TCNQ盐的合成与光谱研究

合成了导电性ＴＣＮＱ盐Ｃｕ（ｐｎ）２（ＴＣＮＱ）ｎ（ｎ＝２和３，ｐｎ＝１，２－丙二胺，ＴＣＮＱ＝７，７，８，８－四氰基对苯二醌二甲烷）。红外光谱、电子光谱和Ｘ－光电子能谱研究表明ＴＣＮＱ盐中存在ＴＣＮＱ°和ＴＣＮＱ－，ＴＣＮＱ°与ＴＣＮＱ－之间发生了部分电子转移，致使铜呈混合价态。它们的粉末室温电导率为１．１×１０－５～２．４×１０－６ｏｈｍ－１ｃｍ－１。     

四硫代富瓦烯/四氰基对二次甲基苯醌单分子膜气-液界面性质及LB膜组装体的紫外可见光谱

几种电子给体（四硫代富瓦烯，ＴＴＦ）、电子受体（长链四氰基对二次甲基苯醌；Ｃ１８ ＴＣＮＱ）及它们相应的 １：１摩尔比复合物的气－液界面分子行为表明：不带长链的 ＴＴＣ１－ ＴＴＦ、ＢＥＤＴ－ＴＴＦ的成膜性在其与Ｃ１８ＴＣＮＱ形成复合物之后均得到显著改善。Ｃ１６ＴＴＦ、Ｃ１８ ＴＣＮＱ及两者不同结构ＬＢ膜组装体的紫外可见光谱研究发现：Ｃ１８ＴＣＮＱ在其单独的Ｙ－型 膜中摩尔吸光系数是７．５×１０３，而在交替组装体中其摩尔吸光系数是１．３×１０３，给受体之间 的相互作用导致跃迁偶极矩减小，从而引起吸光系数减小４倍多。     

两种荧光LB膜的制备和光谱性能

制取了４－二氰基亚甲基－２－甲基－６－对二甲胺基苯乙烯基－４Ｈ－吡喃（ＤＣＭ）和１，２－双（５－甲基苯并恶唑）基乙烯（ＤＴ）两种荧光分子的ＬＢ膜以及两者的混合膜，以吸收光谱和荧光光谱探讨了膜中分子的构型，微环境，发光性能等特征，发现在ＬＢ膜的缀密排布环境中ＤＣＭ顺式构型的含量较之在溶液中大为增加。     

八烷氧基2,3-萘酞菁锌(Ⅱ)的合成及荧光光谱研究

采用在强有机碱１，８－二氮杂双环［５，４，０］＋－－７烯（简称ＤＢＵ）存在下的醇溶剂中，由“分子碎片”与锌盐通过模板反应的新方法合成了一组八烷氧基２，３－萘酞菁锌配合物（Ｚｎ（ＲＯ）８ＮＰｃ，其中Ｒ＝Ｃ４Ｈ９、Ｃ８Ｈ１７、Ｃ１２Ｈ２５，ＮＰｃ＝Ｃ４８Ｈ１６Ｎ８）。产物进行了元素分析和红外光谱分析，并研究了它们在不同溶剂中的荧光光谱。     

2,9,16,23—四硝基酞菁镍（Ⅱ）的合成和光谱性质研究

在强有机碱１，８－二氮杂双环［５．４．０］＋－－７烯（简称ＤＢｕ）存在的醇溶剂中，利用“分子碎片”（４－硝基邻苯二腈）与金属离子通过模板反应的新方法合成了２，９，１６，２３－四硝基酞菁镍（Ⅱ）配合物（简称ＴＮＰｃＮｉ，Ｐｃ＝Ｃ３２Ｈ１２Ｎ８），通过元素分析和ＩＲ光谱进行了表征，研究了配合物在ＤＭＳＯ、ＤＭＦ、Ｐｙ、ＣＨ２Ｃｌ２和Ｃ６Ｈ１２中的电子吸收光谱及荧光光谱。     

酞菁铜（Ⅱ）衍生物的合成及其成膜性

合成了四－４－（８－喹啉氧基）酞菁铜（Ⅱ）等６种新型酞菁铜衍生物，通过元素分析、红外光谱、顺磁共振、质谱及核磁共振谱加以确认。紫外可见光谱表明它们在氯仿溶液（１０＾－５ｍｏｌ／Ｌ）中主要以单分子形式存在，配合物的氯仿溶液在亚相（水）上的π－Ａ曲线表明，它们均有明显的“气－液－固”变化过程，具有良好的形成ＬＢ膜性质。     

稀土（Nd,Pr）（Ⅲ）双酞菁衍生物的合成,表征和气敏特性

合成了八－４－（四氢糖氧基）酞菁钕（Ⅲ）（Ａ）、八－４－（β－萘氧基）酞菁钕（Ⅲ）（Ｂ）、八－４－（２，４－二叔戊基苯氧基）酞菁钕（Ⅲ）（Ｃ）和八－４－（２，４－二叔戊基苯氧基）酞菁镨（Ⅲ）（Ｄ）４种新的稀土（Ｎｄ、Ｐｒ）（Ⅲ）双酞菁衍生物，经元素分析、红外光谱、核磁共振谱表征。紫外可见光谱表明，它们在氯仿（１０＾－６ｍｏｌ／Ｌ）溶液中以单分子形式存在。热重分析证明配合物的热稳定性：Ｂ＞Ｃ￣Ｄ＞Ａ     

铟（Ⅲ）—2—硫基苯骈噻唑—7—碘—8—羟基喹啉—5—磺酸三元络合物吸附波研究

在ＨＣｌ－ＮａＡｃ介质（ｐＨ２．５）中，用单扫示波极谱法可获得高灵敏的Ｉｎ（Ⅲ）－２－巯基苯骈噻唑（ＭＢＴ）－７－碘－８－羟基喹啉－５－磺酸（Ｆｅｒｒｏｎ）三元络合物吸附波，峰电位在一－０．６４Ｖ（ｖｓ．ＳＣＥ），峰电流与铟浓度在７．０×１０＾－１０ｍｏｌ／Ｌ～８．８×１０＾－７ｍｏｌ／Ｌ之间呈线性关系，检出限可达３．０×１０＾－１０ｍｏｌ／Ｌ，测得电活性络合物的组成为Ｉｎ（Ⅲ）：ＭＢＴ：１∶１∶     

含TBP的PS－EC复合膜微胶囊的制备及对Cr_2O_7~（2－）传输的研究

将聚苯乙烯（ＰＳ）和乙基纤维素（ＥＣ）溶于ＣＨ_２Ｃｌ_２中，利用水中干燥法制备ＰＳ－ＥＣ复合膜微胶囊。当复合膜的微孔中含有磷酸三丁酯（ＴＢＰ）时，微胶囊膜对Ｃｒ_２Ｏ_７~（２－）具有传输功能。芯材采用高浓度ＮａＯＨ时，可使Ｃｒ_２Ｏ_７~（２－）逆浓差传输。研究了ＰＳ和ＥＣ的比例、微胶囊粒径、ＮａＯＨ浓度及ＴＢＰ含量对传输的影响．在适当条件下，１０ｍｉｎ内Ｃｒ_２Ｏ_７~（２－）的浓度由１×１０~（－４）ｍｏｌ／Ｌ降至１×１０~（－７）ｍｏｌ／Ｌ以下。     

对叔丁基杯[8]芳烃/钼磷杂多酸纳米杂化LB膜的制备与表征

以含有共轭大π键的对叔丁基杯[8]芳烃(Cal8)和十八(烷)铵(ODA)与Keggin结构和Dawson结构钼磷杂多酸(HPA)做成膜材料, 用LB技术制备了2种新型无机-有机杂化LB膜. 用π-A曲线、UV-Vis吸收光谱、荧光光谱和原子力显微镜(AFM)对标题LB膜的成膜性质、结构及发光性质进行了表征. 结果表明在空气/水界面Cal8/ODA/HPA杂化可形成稳定的单层与多层膜. 标题杂化LB膜的崩溃压为39.0 mN/m, 其粒子具有纳米尺寸, 在激发波长为280 nm时, 可观察到322～387 nm处由Cal8分子π-π*跃迁引起的荧光发射峰及510 nm处 杂多阴离子的配体到金属的荷移跃迁(LMCT)三重发射谱带.     

Natural (−)-7-methoxy-8-(β, γ-dihydroxyisopentyl)-coumarin

Chemistry of Natural Compounds - The roots ofPrangos ferulaceae (L.) Lindl. have yielded (?)-7-methoxy-8-(β, γ-dihydroxyisopentyl)-coumarin, composition C15H18O5, with mp 128°....     

Total synthesis of (-)-(6S,7S,8S,9R,10S,2'S)-membrenone-A and (-)-(6S,7S,8S,9R,10S)- membrenone-B and structural assignment of membrenone-C

[reaction: see text] (-)-(6S,7S,8S,9R,10S,2'S)-Membrenone-A and (-)-(6S,7S,8S,9R,10S)-membrenone-B were prepared in 11 steps (3% and 2.4% overall yield, respectively). Key steps included a tin(II)-mediated aldol followed by a syn selective reduction, giving the C7-C9 stereocenters, a second chain extending aldol coupling, and a p-TsOH-promoted cyclization/dehydration giving the common gamma-dihydropyrone precursor. We have thus established that synthetic (-)-(6S,7S,8S,9R,10S,2'S)-membrenone-A, (-)-(6S,7S,8S,9R,10S)-membrenone-B, and (-)-(6S,7S,8S,9R,10S)-membrenone-C are the enantiomers of the natural products.     

Thermal behavior of H-aggregate in a mixed Langmuir-Blodgett film of merocyanine dye, arachidic acid, and n-octadecane ternary system investigated by UV-visible and IR absorption spectroscopy

We have investigated the thermal behavior of H-aggregate in a mixed Langmuir-Blodgett (LB) film of the merocyanine dye (MS18)-arachidic acid (C20)- n-octadecane (AL18) ternary system by means of UV-visible and IR absorption spectroscopy in the range from 25 to 250 degrees C with a continuous scan. The results of both UV-visible and IR spectra indicate that the temperature-dependent variation in MS 18 aggregation state is linked not only with the degree of intramolecular charge transfer and the behavior of packing, orientation, conformation, and thermal mobility of the MS18 hydrocarbon chain but also with the presence and absence of AL18. The H-aggregate dissociates from 25 up to 50 degrees C, which is caused by the AL18 evaporation from the mixed LB film and the increment of thermal mobility of the MS18 hydrocarbon chain. From 110 to 160 degrees C, blue-shifted bands, attributed to the oligomeric MS18 aggregation, appear near 515 nm in the MS18-C 20-AL18 ternary system as well. The temperature at which the 515 nm band occurs is identical for both present ternary system and previously investigated MS18-deuterated arachidic acid (C20- d) binary system, and it is in good agreement with the melting point (110 degrees C) of cadmium arachidate (CdC20). Therefore, it is indicated that the driving force which induces the 515 nm band comes from the melting phenomenon of CdC20 molecules which are phase-separated from MS 18 molecules in as-deposited LB films.     

4-[2-(9,10-二氰蒽)乙烯基]-N-甲基-N-十六烷基苯胺的合成及其吸收光谱行为的研究

通过还原、溴代、氰化、Wittig反应等七步反应设计合成了一新二元电子给体－受体（D－A）化合物：4－［2－（9，10－二氰蒽）乙烯基］－N－甲基－N－十六烷基苯胺（DCACMA，反式）并初步研究了其吸收光谱行为。研究表明，基态下DCACMA分子中电子给体与电子受体（CMA与DCA）间存在显著的电荷转移相互作用，在LB膜及簇集态（DMSO－H2O二元体系中）下，DCACMA分子呈H－型簇集排列。     

Thermal behavior of J-aggregates in mixed Langmuir-Blodgett films composed of merocyanine dye and deuterated arachidic acid investigated by UV-visible and infrared absorption spectroscopy

We have investigated the thermal behavior of J-aggregates in the mixed Langmuir-Blodgett (LB) films composed of the merocyanine dye (MS18)-deuterated arachidic acid (C20-d) binary system in the temperature range from 25 to 250 degrees C by means of UV-visible and IR transmission absorption spectroscopy. The temperature-dependent variations in both UV-visible and IR absorption spectra indicate that the MS18 aggregation states are linked with the MS18 intramolecular charge transfer and the behavior of the packing, orientation, conformation, and thermal mobility of the MS18 hydrocarbon chain. The J-aggregate formed at 25 degrees C in the mixed LB films dissociates in the temperature range from 25 to 110 degrees C, which is mainly ascribed to the increase in the thermal mobility of MS18 hydrocarbon chain and the dissociation of the chelation by a cadmium ion to the MS18 keto group. A thermally induced blue-shifted band appears at around 515 nm from 110 to 160 degrees C. This band is attributed to oligomeric aggregation with side-by-side alignment of the MS18 transition dipole moments on the basis of the shift to a higher-energy side, broadening, and temporary increment of the MS18 intramolecular charge transfer of the band. Consequently, the appearance of the thermally induced blue-shifted band indicates the possibility that the MS18 aggregation states can be controlled from the red shift to the blue shift by the annealing method adopted in the present study.     

Valence isoelectronic substitution in the B8(-) and B9(-) molecular wheels by an Al dopant atom: umbrella-like structures of AlB7(-) and AlB8(-)

The structures and the electronic properties of two aluminum-doped boron clusters, AlB(7)(-) and AlB(8)(-), were investigated using photoelectron spectroscopy and ab initio calculations. The photoelectron spectra of AlB(7)(-) and AlB(8)(-) are both broad, suggesting significant geometry changes between the ground states of the anions and the neutrals. Unbiased global minimum searches were carried out and the calculated vertical electron detachment energies were used to compare with the experimental data. We found that the Al atom does not simply replace a B atom in the parent B(8)(-) and B(9)(-) planar clusters in AlB(7)(-) and AlB(8)(-). Instead, the global minima of the two doped-clusters are of umbrella shapes, featuring an Al atom interacting ionically with a hexagonal and heptagonal pyramidal B(7) (C(6v)) and B(8) (C(7v)) fragment, respectively. These unique umbrella-type structures are understood on the basis of the special stability of the quasi-planar B(7)(3-) and planar B(8)(2-) molecular wheels derived from double aromaticity.     

7,7-二甲基-2-对溴苯基-4-苯基-5-氧代-1,4,5,6,7,8-六氢化-6H-喹啉的合成及晶体结构

标题化合物C23H22BrNO是由1-(4-溴苯基)-3-苯基-2-丙烯-1-酮与5,5-二甲基-1, 3-环己二酮在N, N-二甲基甲酰胺(DMF)中在NH4OAc催化下反应而得。结构通过单晶X-射线衍射分析确定,其晶体属于单斜晶系,空间群C2/C, a = 19.678(4),b = 13.571(2),c = 17.311(3) 牛琤 = 118.74(1),Mr = 408.33, V = 4055(1) ?,Dc = 1.338 g/cm3, Z = 8, m (MoKa) = 2.038 mm-1, F(000) = 1680, R = 0.0539,wR = 0.1369。X-衍射分析表明,六元环C(10)C(13)C(16)C(17)采用半椅式构象:原子C(10),C(11),C(12),C(16)和C(17)在同一个平面内,而原子C(13)远离平面为0.3282 牛闷矫嬗?个苯环的夹角分别为41.09, 81.97,2个苯环的夹角为75.87。另外在晶体结构中,存在1个分子间氢键。     

Luminescent Langmuir-Blodgett films of platinum(II) complex [Pt(L18)Cl](PF6) (L18 = 2,6-bis(1-octadecylbenzimidazol-2-yl)pyridine)

A novel amphiphilic Pt complex containing 2,6-bis(1-octadecylbenzimidazol-2-yl)pyridine (L18), [Pt(L18)Cl](PF6), has been synthesized. The complex exhibits concentration-dependent absorption and emission spectra in solution. With increasing the concentration of the Pt complex, we observed a new absorption band centered at 550 nm derived from a metal-metal d sigma* to ligand pi* charge transfer (MMLCT) transition and the corresponding broad emission centered at 650 nm. The Pt complex is surface-active, and the surface pressure-area isotherm reveals three phase transitions. The three phases correspond to one liquid-expanding phase and two solid-condensed phases, respectively, with different intermolecular overlap in the "flat-on" orientation at the air-water interface. Without additives such as fatty acids, the complex forms a stable and reproducible Langmuir-Blodgett (LB) multilayer film above a surface pressure of 15 mN m-1. Strong emission from the LB films, even monolayer, was observed. Comparing the relative emission intensity of the MMLCT band for transferred LB monolayer film with that for cast films, we concluded that Pt-Pt interactions are suppressed in the LB film. Instead, the emission at 600 nm arising from the ligand-ligand pi-pi interacted excited state became dominant. The results would provide the insight into the control of molecular ordering for planar Pt complexes from the viewpoint of characteristic excited states.     

Synthesis of 7-[4-alkoxy-3-methoxy(hydroxy)phenyl]-10,11-dihydrobenzo[c]acridin-8(7H,9H,12H)-ones and 4-(8-oxo-7,8,9,10,11,12-hexahydrobenzo[c]acridin-7-yl)-2-methoxy(ethoxy)phenyl esters of carboxylic acids

Reactions of azomethines (Schiff bases) prepared from vanillin and vanillal ethers and 1-naphthylamine with cyclohexane-1,3-dione in butanol afforded in 40–64% yields 7-[4-alkoxy-3-methoxy(hydroxy)phenyl]-10,11-dihydrobenzo[c]acridin-8(7H,9H,12H)-ones and 4-(8-oxo-7,8,9,10,11,12-hexahydrobenzo[C]acridin-7-yl)-2-methoxy(ethoxy)phenyl esters of carboxylic acids. The reaction products presumably formed by the rearrangement of the azomethine adduct with the cyclohexane-1,3-dione proceeding by the type of Hofmann-Martius rearrangement. The structure of compounds synthesized was confirmed by the elemental analysis, UV, IR, and ¹H NMR spectra.