曙红与卟啉分子间和分子内的光致相互作用

合成了以半刚性链(一CH_2phCH_2—)和柔性链(—(CH_2)_4—)连接的曙红-卟啉二元化合物及其模型化合物.通过吸收光谱、荧光光谱、激发光谱及荧光寿命研究了模型化合物分子间的相互作用和二元化合物分子内的光致电子转移和能量传递.结果表明:二元化合物的模型化合物曙红乙酯和卟啉易形成基态复合物 在二元化合物分子内激发曙红时,曙红能将其单重态能量传递给卟啉,并能引发分子内的电子转移;激发卟啉时,能发生曙红向卟啉的电子转移.分析了分子构型和溶剂极性对2种过程的影响.     

3,6-二(3-苯基-1,3-丙二酮基)-9-乙基咔唑的合成、光谱性质与量子化学研究

咔唑分子经SN1烷基化、Friedle-crafts双乙酰化和Claisen缩合3步反应,合成了一种新颖的双β-二酮化合物9-乙基-3,6-二(3-苯基-1,3-丙二酮基)咔唑,对其结构进行了元素分析、IR、1H NMR和MS表征.研究了中间体和目标化合物的吸收光谱性质,采用密度泛函理论在B3LYP/6-31G*水平上对目标化合物基态结构进行优化,运用含时密度泛函理论在相同水平上计算了吸收光谱数据,从微观上分析了化合物的电子跃迁行为.     

曙红酯与紫精的分子内及分子间的电子转移

合成了以—(CH_2)_1O.—相连的曙红和丁基紫精的二元化合物,运用吸收光谱,荧光光谱及荧光寿命,研究了分子间及分子内的光致电子转移过程,及加入β-环糊精或糖淀粉对二元化合物体系的影响.结果表明:分子内比分子间的作用显著增强,加入环糊精或糖淀粉后,其与二元化合物形成包结络合物,使电子转移的过程得到改变.     

新型双螺噁嗪分子的合成及性能

设计合成了3个双螺噁嗪化合物, 采用核磁共振谱、红外光谱和高分辨质谱对这些化合物进行了表征. 测试了光照前后化合物在不同溶剂中的紫外吸收光谱、荧光光谱以及在高分子薄膜中的消色动力学曲线. 结果表明, 目标化合物均具有良好的光致变色性能和耐疲劳度, 在材料、分子开光及生物探针领域有潜在的应用前景.     

三芳基-2-吡唑啉化合物分子内光诱导电荷转移过程的研究

本工作对带有不同取代基的1,3,5-三芳基-2-吡唑啉类化合物的稳态光物理行为进行了研究,从它们在不同极性溶剂中的吸收光谱和荧光发射光谱以及荧光量子效率的结果表明,这类化合物分子内共轭的及非共轭的光诱导电荷转移的趋向取决于上述两过程间的竞争。     

非平面分子内共轭电荷转移化合物的发光行为

合成了两种分子内共轭的电荷转移化合物:2,3二氰基-5,7-二[2-[(4-二甲氨基)-苯基]乙烯基]-6H-1,4-二氮杂卓(1)及2,3-二氰基-5-苯基-7-[2-[(4-二甲氨基)-苯基]乙烯基]-6H-1,4-二氮杂卓(2). 用UV-Vis吸收光谱和荧光光谱法对它们在不同极性溶剂中的光致变色行为进行了研究.结果表明，化合物的荧光最大发射波长与溶剂的极化参数ET(30)值可在一定范围内构成线性关系，而单臂共轭的化合物2比双臂共轭的化合物1有着更大的Stoke’s位移和基态/激发态偶极矩差.对得到的结果进行了初步的讨论.     

取代苯乙烯基吡嗪光物理行为的研究

合成了一系列带有不同推，拉电子能力的取代本乙烯基吡嗪化合物，测定了它们在不同极性，不同粘度介质条件下的吸收光谱和发射光谱，结果表明，异构化和邻近效果导致该类化合物荧光量子产率较低的主要原因，而取代基的性质对它们的发光行为以及光异构化行为均有很大影响。     

取代苯乙烯基吡嗪光物理行为的研究

合成了一系列带有不同推、拉电子能力的取代苯乙烯基吡嗪化合物，测定了它们在不同极性、不同粘度介质条件下的吸收光谱和发射光谱．结果表明，异构化和邻近效应是导致该类化合物荧光量子产率较低的主要原因，而取代基的性质对它们的发光行为以及光异构化行为均有很大影响     

新型含二茂铁基螺噁嗪类光致变色化合物的合成及其光谱研究

合成了一种新的含二茂铁基螺噁嗪类光致变色化合物，并研究了其吸收光谱和荧光光谱。发现在分子内引入二茂铁基团提高了热不可逆性，发生光致变色反应前后化合物结构的不同对其荧光特性影响很大。     

高效液相色谱-在线消解-氢化物发生原子吸收光谱联用技术研究

运用自行设计的接口，实现了高效液相色谱与原子吸收光谱的联用。通过对常见砷化合物进行形态分忻，考察了自行设计的高效液相色谱＋紫外在线消解-氢化物发生原子吸收光谱联用（HPLC—UV—HGAAS）接口的性能。实现了将分离后不能直接用于氢化物发生的大分子，通过紫外“在线”消解成小分子砷化合物的目的。确定了仪器的最优化分析条件。建立了快速、直接、连续、在线的HPLC-UV-HGAAS元素形态分析方法。     

Study of spectral and fluorescent properties and isomerization of merocyanines containing nitrile groups as acceptors

The spectral, fluorescent, and photochemical properties of new merocyanines containing nitrile groups as acceptors have been studied. Positive solvatochromism is observed for most of these compounds; however, for the dye containing three nitrile groups as acceptors—polyenic aminotrinitrile—negative solvatochromism is observed: the absorption spectrum is shifted to shorter wavelengths with increasing the solvent polarity. In all solvents used, the fluorescence and fluorescence excitation spectra of the merocyanines almost do not depend on the excitation and fluorescence registration wavelengths, respectively. Using the flash photolysis method, the formation of photoisomers of the merocyanines has been detected and the kinetics of their decay in solvents of different polarity has been studied. Backward (dark) isomerization of the photoisomers has been shown to take place more slowly in nonpolar solvents.     

INDO/SCF-CI calculations and structural spectroscopic studies of some complexes of 4-hydroxyacetanilide

The electronic energies among different possible structures of 4-hydroxyacetanilide (paracetamol) (PA) molecule, were calculated using INDO method and it has been concluded that its structure has C(s) point group symmetry of the cis-form. The ionization potential, electron affinity, dipole moment and binding energy have been calculated. The calculated electronic transitions of the cis-form of PA using SCF-CI method have good coincidence with the electronic absorption spectrum. The temperature effect on the electronic spectrum of PA confirms the presence of one conformer only. The electronic spectra of PA compound were studied in different polar- and non-polar solvents and the hydrogen bonding as well as the orientation energies of the polar solvents were determined from the mixed solvents studies. Complexes of PA with various metal ions such as, Cu(II), Zn(II) or Fe(II) ions of ratio 2:1, respectively, have been prepared and their structure has been confirmed by elemental analysis, atomic absorption spectra, IR spectra and (1)H NMR spectra and finally it can be concluded that the structure of the complexes has C2h point group symmetry in which two PA molecules are chelated to any one of the metal ions, Cu(II), Zn(II) and Fe(II) ions.     

对-羟基苄叉丙二腈溶液在不同pH条件下吸收光谱的变化

在苄叉丙二腈衍生物系列中,N,N-二烷基氨基苄叉丙二腈及其类似化合物是研究和应用较多的一类。它们曾作为分子探针应用于高分子微环境特性和高分子聚合过程的研究。作为一种分子内的电荷转移络合物,它们在不同溶剂中的光谱行为也进行过研究,从而为进一步的开拓应用提供了重要依据。和前者相比,对-羟基苄叉丙二腈无论在基础研究或实际应用上都显得比较薄弱。正因如此,本工作合成了该化合物并对它进行了初步研     

N-萘甲基多乙撑多胺类荧光化学敏感器

荧光化学敏感器（ＦｌｕｏｒｅｓｃｅｎｃｅＣｈｅｍｉｃａｌＳｅｎｓｏｒ,ＦＣＳ）是近年来得到迅速发展用以检测外来物种的一种新方法．一般说来,它由下列三个部分所组成：（１）外来物种的接受体部分,（２）荧光发射部分,（３）连接体部分．作为接受体部分的设计是决定ＦＣＳ在检测物种时的选择性或专一性的关键所在．因此其设计往往要和拟检测物种的结构特征相联系．荧光发射部分的选定则和ＦＣＳ的灵敏度相关,适当的选择会使ＦＣＳ的接受体在接受外来物种后,能灵敏地引起荧光发射强度或特征发射波长的变化,使人们可敏锐地发觉所…     

Synthesis and Properties of Copper Tetra-4-lauryloxyphthalocyanine

Copper tetra-4-lauryloxyphthalocyanine was synthesized. Its electronic absorption spectra show that the complex is associated in organic solvents. The shape of the spectrum and the positions of the absorption bands are virtually independent of the solvent. The compound exhibits thermotropic and lyotropic mesomorphism.     

The study of enantioselectivity in copper complexes with some 1,3-dicarbonyl ligands by circular dichroism spectroscopy

The circular dichroism spectra of copper(II) complexes with hydroxymethylene camphor, hydroxymethylene menthone, and trifluoroacetyl camphor as well as of mixed-ligand complexes with acetylacetone have been studied in different solvents at different temperatures. The changes observed in the spectra are attributed to a strong coordination of the solvent molecules in axial positions of square-planar complexes. It has been shown that the contributions of two ligands to the net spectrum of circular dichroism are additive and that the absorption spectra of the complexes do not depend on the optical configuration of the ligands. The conclusion has been drawn that no noticeable inter-ligand interactions exist in the complex and no enantioselective effects are exhibited.     

The electronic spectra and excited state dipole moment of 2-fluoropyridine

The electronic absorption spectrum in the vapour state and in solution in different solvents in the region 3000–1900 Å and the fluorescence and phosphorescence emission spectra in ethanol or cyclohexane at 77 K have been studied for 2-fluoropyridine and analysed. Two systems of absorption band corresponding to the π→π* transition II and π→π* transition III have been observed and the excited state dipole moments have been determined from the solvent-induced shifts of the electronic absorption bands. The half-life of phosphorescence in cyclohexane at 77 K is found to be 3.5 s.     

The EPR spectra of copper compounds with tetragonal symmetry in glasses

The conditions for the appearance of the additional absorption peak and its position in the EPR spectra of copper compounds with tetragonal symmetry in glasses have been analyzed. It has been found that the constants of the spin hamiltonians A and B should always have negative signs. The resulting theoretical conclusions have been compared with experimental results on the EPR of bis(salicylideneiminato)copper in various solvents and low-temperature glasses.     

Thermo-dynamical contours of electronic-vibrational spectra simulated using the statistical quantum�Cmechanical methods

Three polycyclic organic molecules in various solvents focused on thermo-dynamical aspects were theoretically investigated using the recently developed statistical quantum mechanical/classical molecular dynamics method for simulating electronic-vibrational spectra. The absorption bands of estradiol, benzene, and cyanoanthracene have been simulated, and most notably, the increase in the spectral intensity for the lowest excited state transition as the temperature is increased observed experimentally is well reproduced. In addition, this method has been extended to treat luminescent processes also, and it is seen that the experimental emission spectrum of cyanoanthracene is also well described. The method still needs further refinement, but results to date, including those presented in this work, document clearly that our model is one which is able to treat the many complex effects that the environment have on electronic absorption and emission spectra.     

疏水作用对光化学和光物理过程的影响 Ⅻ.2-羟基-4-烷氧基二苯甲酮在不良溶剂中的簇集

测定了2-羟基-4-甲氧基二苯甲酮(HMDB)和2-羟基-4-辛氧基二苯甲酮(HODB)在良溶剂和不良溶剂中的吸收光谱。在不良溶剂(乙二醇-水的混合溶剂)中,带长链的HODB发生簇集。由于簇集体内极性较小,HODB的吸收光谱与其在环己烷中相似。HMDB不发生簇集。