可逆逐级电子转移过程的1.5次和2.5次微分新极谱法

本文提出了可逆逐级电子转移过程(n_1=n_2)的1.5次和2.5次微分电分析法(卷积伏安法)的理论公式,用计算机绘出了相应的理论曲线图,讨论了标准分离电位(△E~0)及电子转移数(n)对电流～电压曲线的影响.选用氯化铜(Ⅱ)-氨水-氯化铵体系进行了实验验证,其结果与理论完全相符.     

三氰基乙烯基甲基咔唑的光物理性质──能级邻近效应和溶剂化显色效应

在许多含氮杂环和芳香族拨基化合物中,能量最低的nπ^*态与能量最低的ππ^*态能级非常接近,这种能级分布往往导致nπ^*态和ππ^*态中能量较低的一个激发态的有效的无辐射失活。这就是能级邻近效应。这种效应被认为是nπ^*和ππ^*两能级间振动相互作用的结果。     

Syntheses and structures of new luminescent B(III) complexes: BPh2(2-(2-pyridyl)naphtho[b]imidazole) and BF2(2-(2-pyridyl)naphtho[b]imidazole)

A novel chelating ligand, 2-(2-pyridyl)naphtho[b]imidazole (PNI) has been synthesized and structurally characterized. The PNI molecule reacts readily with BPh₃ and BF₃ to form BPh₂(2-(2-pyridyl)naphtho[b]imidazole) (1) and BF₂(2-(2-pyridyl)naphtho[b]imidazole) (2), respectively. The structures of PNI and 1 were determined by single crystal X-ray diffraction, while that 2 by spectroscopic methods. The structure of 1 reveals that the boron center is four-coordinated. The electroluminescent device using 1 as the emitting layer shows bright yellow luminescence with a maximum emission peak at 540 nm. Complexes 1 and 2 form a new family of organometallic emitting materials which could be of interest for practical applications.     

4′-(二茂铁基)-2,2′∶6′,2″-三联吡啶钴(Ⅱ)配合物混合价态的电荷转移

设计合成了4′-(二茂铁基)-2,2′∶6′,2″-三联吡啶钴(Ⅱ)配合物1以及参比配合物4′-(4-甲苯基)-2,2′∶6′,2″-三联吡啶钴(Ⅱ)配合物2和2,2′∶6′,2″-三联吡啶钴(Ⅱ)配合物3,配合物1中二茂铁基给电子基团的引入使其在可见光区的吸收明显增强,并在部分氧化时呈现混合价态的电荷转移(MVCT)吸收.     

Dual fluorescence of omeprazole: effect of solvents and pH

Absorption, steady state fluorescence and time-resolved fluorescence spectra of omeprazole (OMP) have been studied in solvents of different polarity and pH. With an increase in the polarity of the solvents, blue shift is observed in the longer wavelength whereas red shift is noticed in the shorter wavelength band. The dual emission observed in non-polar solvents suggests that the energy of the twisted intramolecular charge transfer (TICT) state is lower than that of the locally excited (LE) state. The normal Stokes-shifted band originates from the LE state, and the large Stokes-shifted band is due to the emission from a TICT state. The Stokes shift of OMP is correlated with various solvent polarity scales like E_T(30) and f?(D,n).     

7-甲氧基香豆素-3-甲酰二乙醇胺的电子结构和光谱性质的理论研究

采用密度泛函的B3LYP和单激发组态相互作用(CIS)方法分别对基态和第一、第二单重激发态(S1和S2)结构进行优化,均采用6-31G(d)基组.在优化的基态和第一单重激发态的结构基础上,用含时密度泛函理论(TD-DFT),成功模拟了7-甲氧基香豆素-3-甲酰二乙醇胺的吸收光谱和荧光发射光谱,并用极化连续模型考虑了溶剂的影响.利用前线轨道、电荷密度差(CDD)和态密度(DOS)图分析了电子跃迁的特性.计算结果与实验结果吻合得很好.该量子计算方法对此类化合物的定性和定量研究是有效的.     

交叉共轭型烯酮化合物分子内的电荷转移

近年来有关分子内电行转移化合物的设计、合成及其光谱、光物理并为的研究引起＾们极大的兴趣[1－4]．这类化合物在激发态时常表现出一些特殊的性能，如出现扭曲的分子内电行转移（TICT）现象，并在荧光光谱中出现奇特的K重发光和在荧光强度与温度的依赖关系上出现反常等[5]．TICT态的形成强烈的依赖于化合物分子本身的结构，屯依赖于化合物分子所处环境的极性、温度和粘度等因素同．带有强给电子基（CH3卜N烁酮类化合物是一类有效的光敏剂．它广泛的应用于如光引发聚合、全息成像[7-8]等不同领域．同时其光谱及光物理行为的研究也已兑…     

A Novel Proton Sensor with Luminescence and Color Signaling Based on Platinum（Ⅱ） Terpyridyl Acetylide Complex

A novel sensitive probe for proton based on platinum(Ⅱ) terpyridyl acetylide complex by monitoring the changes both in luminescence and color is described.     

Synthesis and optoelectronic characterization of poly(fluorenylethynylene)s containing perylene bisimide moiety in the backbone

A series of poly(fluorenylethynylene)s containing different ratios of perylene bisimide moiety in the backbone were synthesized by Sonogashira cross‐coupling reaction. The electron‐deficient perylene bisimide moiety was introduced into the backbone to construct the donor‐acceptor architectures. The chemical structures of these copolymers were determined by ¹H NMR and FTIR. The solubility, thermal, and optoelectronic properties were studied. The results of UV–vis absorption and fluorescence spectra of these copolymers showed that intramolecular energy transfer and charge separation occur between the fluorenyl alkyne segment and perylene bisimide moiety. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1932–1938, 2008     

基于荷移反应的高效液相色谱法测定氨基丁醇

建立了一种基于荷移反应的高效液相色谱测定氨基丁醇含量的分析方法。在pH 8.4的硼砂-硼酸缓冲溶液中,氨基丁醇与四氯苯醌于60℃反应60 min,利用高效液相色谱法-紫外检测器进行分析。荷移络合物采用Agilent Extend C18色谱柱（250 mm×4.6 mm,5 μm）分离,以0.001%（体积分数）三乙胺甲醇溶液为流动相进行梯度洗脱,流速为1 mL/min,检测波长为350 nm。该方法对氨基丁醇的定量限为0.01 g/L,线性范围为0.1~0.6 g/L,相关系数（R²）为0.9994;方法的加标回收率为98.3%~103.6%,相对标准偏差（RSD）为0.9%~1.6%。该法简便快捷,适用于氨基丁醇含量的快速检测。     

含茂铁基三联吡啶钌功能分子的光电性质*

多吡啶钌配合物在光化学、光物理、电化学、电子转移、能量转移、分子组装和分子识别等研究领域都扮演着非常重要的角色。茂铁基具有化学稳定性、氧化还原活性、富电子性和结构易修饰等特点,使其在功能分子的设计与合成等领域得到广泛的应用。结合茂铁的电化学活性和[Ru(tpy)₂]²⁺的光学活性,在[Ru(tpy)₂]²⁺分子中三联吡啶的4′位上引入茂铁基,可以构筑性能优良的光电功能分子。本文介绍了近年来含茂铁基（尤其是具有扩展共轭体系的茂铁炔基或茂铁苯炔基）三联吡啶钌光电功能分子的研究进展,并结合本课题组的研究成果探讨了炔基的引入、炔基位置的不同和炔基长度（由单炔基到双炔基）的变化对该类化合物光电性质的影响。     

新型有机电双稳态材料的设计和性质

本文旨在突破传统的TCNQ和TTF的分子架构，通过分子剪裁保留这两个分子中的核心功能基团，同时引入新的螺环分子骨架以提高分子的热稳定性，从而获得全新的具有电子授受性质的有机化合物，并研究其电荷转移配合物的电双稳性质。     

3,6-二(蒽醌-2-乙烯基)-N-乙基咔唑的合成及光谱性质研究

利用N-乙基咔唑和2-甲基蒽醌合成了一种A-π-D-π-A分子内电荷转移型化合物3,6-二(蒽醌-2-乙烯基)-N-乙基咔唑,并对该化合物的光化学和光物理行为进行了研究。荧光光谱表明,该化合物的发光行为对溶剂的极性非常敏感,随着溶剂极性的增大,其荧光最大发射峰有明显红移,并在强极性溶剂乙腈中出现了双荧光现象。该化合物的激发态和基态的偶极矩差值△μ为3.014D,发生了从给体(咔唑基)的N原子到分子两端受体(蒽醌)的羰基的分子内电荷转移。     

Anion-Coordination-Assisted Assembly of Supramolecular Charge-Transfer Complexes Based on Tris(urea) Ligands

Charge-transfer (CT) complexes, formed by noncovalent bonding between electron-rich (donor, D) and electron-deficient (acceptor, A) molecules (or moieties) have attracted considerable attention due to their fascinating structures and potential applications. Herein, we demonstrate that anion coordination is a promising strategy to promote CT complex formation between anion-binding, electron-rich tris(urea) donor ligands (D) and electron-deficient viologen cation acceptors (A), which form co-crystals featuring infinite ⋅⋅⋅DADA⋅⋅⋅ or discrete (circular DADA or three-decker DAD) π-stacking interactions. These CT complexes were studied by X-ray diffraction, UV/Vis spectroscopy, electric conductivity measurements, charge displacement curve (CDC) calculations, and DFT computations.     

醚的初始暗氧化反应机理的研究

有机化合物的空气氧化是一个历史悠久的研究课题。早在1851年Schonbein[1]就注意到醚在空气中会被氧化产生过氧化物。本世纪初,Clover和Milas分析了醚的空气氧化产物,并且对醚的氧化机理,进行了研究。     

Donor-acceptor molecules containing thiophene chromophore: synthesis, spectroscopic study and electrogenerated chemiluminescence

Donor-acceptor molecules containing thiophene chromophore with remarkably large Stokes shift (>210 nm) have been found to exhibit strong and stable ECL emission via the singlet excited state without the addition of any co-reactant or a second compound.     

螺芴/2,8-S,S-二氧-二苯并噻吩共聚物的合成与性能

将缺电子单元-S,S-二氧-二苯并噻吩(SO)以2,8位引入到聚螺芴(PSFs)的主链,通过Suzuki聚合得到一系列具有不同SO含量的共聚物PSF-28SO-3、PSF-28SO-5、PSF-28SO-7和PSF-28SO-10。 不同于3,7位连接,该系列2,8-位连接的共聚物既有来自于高分子主链的本征态(LE:local excited)发光,又有来自于从四烷氧基芴侧链到主链中SO单元的电荷转移(CT:charge transfer)发光,最终表现为近白光发射。 其中,PSF-28SO-10具有最优器件性能,发光效率为0.58 cd/A,色坐标为（0.25,0.36）。     

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。     

Color-Tunable Indolizine-Based Fluorophores and Fluorescent pH Sensor

A new fluorescent indolizine-based scaffold was developed using a straightforward synthetic scheme starting from a pyrrole ring. In this fluorescent system, an N,N-dimethylamino group in the aryl ring at the C-3 position of indolizine acted as an electron donor and played a crucial role in inducing a red shift in the emission wavelength based on the ICT process. Moreover, various electron-withdrawing groups, such as acetyl and aldehyde, were introduced at the C-7 position of indolizine, to tune and promote the red shift of the emission wavelength, resulting in a color range from blue to orange (462–580 nm). Furthermore, the ICT effect in indolizine fluorophores allowed the design and development of new fluorescent pH sensors of great potential in the field of fluorescence bioimaging and sensors.