FTIR－PAS技术在卟啉类化合物中的应用（Ⅳ）──稀土乙酰丙酮－meso－四－（α－萘基）四苯并卟啉配合物的红外光谱

研究了ｍｅｓｏ－四－（α－萘基）四苯并卟啉及其Ｄｙ，Ｈｏ，Ｅｒ，ＴＭ，Ｙｂ，Ｌｕ乙酸丙酮形成的配合物在３６００～２２０ｃｍ－１范围内的傅里叶变换红外光声光谱（ＦＴＩＲ－ＰＡＳ），对主要谱带进行了经验归属。结果表明，四－（ａ－萘基）四苯并卟啉与稀土乙酰丙酮配合物中稀土金属离子配位削弱了乙酰丙酮环上Ｍ—Ｏ键的伸缩振动，使此谱带向低波数位移。金属敏感港带出现在～１５１３，～１３２３～１０９０，１０５３和～２５０ｃｍ－１。     

Theoretical study of the optical and charge transport properties in non-peripherally octasubstituted phthalocyanine–tetrabenzoporphyrin hybrids

The charge transfer rate of seven non-peripherally phthalocyanine–tetrabenzoporphyrin hybrids was investigated theoretically at the level of B3LYP/6-31+G(d,p) using density functional theory. The results showed that the hybrids are semiconductor molecules, which have a certain absorption in the visible region. The hole or electron transport capability of a non-peripherally substituted octamethyl phthalocyanine molecule is obviously better than that of phthalocyanine or non-peripherally substituted octafluorine, octamethoxy phthalocyanine molecules at 300 K, whereas the holes or electron transport capabilities of four non-peripherally substituted octamethoxy phthalocyanine–tetrabenzoporphyrin hybrids are basically the same. Overall, the hole transport capability of hybrids is superior to their electron transport capability. The charge transfer rate constant and the carrier mobility rate of three representative molecules using three methods, that is the long range-corrected functionals CHB-B3LYP and WB97XD, the metahybrid GGA M06-2X functional, are consistent with the use of the density functional B3LYP method.     

meso-苯基四苯并卟啉锌的合成和光谱性能的研究

四苯并叶琳(TBP)及其金属配合物是一类新型的光敏性分子,其0-0跃迁出现在λ_max大于630nm的红光区,在光功能材料方面显示出良好的应用前景^[1-2].虽然有关meso-四取代四苯并叶琳金属配合物的合成及其光谱性能的研究已有多篇报道^[3-8],但报道方法的产率较低(最高达15%^[7],有关的光谱性能的报道也不一致^[3-5]。     

固相反应合成卟啉类配合物

固相反应合成卟啉类配合物刘国发，滕永富，师同顺（吉林大学化学系，长春，１３００２３）关键词乙酰丙酮，四苯基取代卟啉，四萘基四苯并卟啉，稀土配合物镧系卟啉配合物是通过在高沸点溶剂或熔融咪唑中反应并进行较为复杂的分离和纯化后而得到的［１］．由于合成条件苛...     

H2TP(o-NO2)TBP及其锌和钴配合物的光谱电化学研究

采用循环伏安以及电化学和电子吸收光谱联用技术研究了邻硝基四苯并卟啉（H2TP（o-NO2)TBP）及其锌和钴配合物在DMF介质的中氧化和还原性质。结果表明H2TP（o-NO2)TBP及其锌配合物的氧化和还原均发生于卟啉的大环π电子结构,伴随有紫外-可见光谱的明显变化,氧化和还原过程为可逆。钴配合物的第一氧化和还原均发生于中心金属离子,第二氧化发生于卟啉的大环π电子结构。     

四萘基四苯并卟啉钴的合成,表征和电化学行为

合成了四萘基四苯并卟啉钴配合物（ＴＮＴＢＰＣｏ）．用元素分析、紫外可见光谱、红外光声光谱，核磁共振氢谱、摩尔电导进行了表征．用循环伏安法研究了ＴＮＴＢＰＣｏ的电化学性质．结果表明，钴卟啉配合物中心离子由正三价还原为正二价的半波电位为－０．２５５Ｖ，由正二价还原为正一价的半波电位为－１．１７５Ｖ，卟啉环还原的半波电位为－１．８５０Ｖ，三步电极反应均可逆．     

Room temperature phosphorescence in the liquid state as a tool in analytical chemistry

A wide-ranging overview of room temperature phosphorescence in the liquid state (RTPL¹) is presented, with a focus on recent developments. RTPL techniques like micelle-stabilized (MS)-RTP, cyclodextrin-induced (CD)-RTP, and heavy atom-induced (HAI)-RTP are discussed. These techniques are mainly applied in the stand-alone format, but coupling with some separation techniques appears to be feasible. Applications of direct, sensitized and quenched phosphorescence are also discussed. As regards sensitized and quenched RTP, emphasis is on the coupling with liquid chromatography (LC) and capillary electrophoresis (CE), but stand-alone applications are also reported. Further, the application of RTPL in immunoassays and in RTP optosensing—the optical sensing of analytes based on RTP—is reviewed. Next to the application of RTPL in quantitative analysis, its use for the structural probing of protein conformations and for time-resolved microscopy of labelled biomolecules is discussed. Finally, an overview is presented of the various analytical techniques which are based on the closely related phenomenon of long-lived lanthanide luminescence. The paper closes with a short evaluation of the state-of-the-art in RTP and a discussion on future perspectives.     

中位－四（邻－硝基苯基）四苯并卟啉及其d过渡金属配合物的电化学性质

用微电极技术和循环伏安法研究了中位－四（邻硝基苯基）四苯并卟啉［ＴＰ（ｏ－ＮＯ＿２）ＴＢＰ］及其Ｆｅ（Ⅲ）、Ｃｏ（Ⅱ）、Ｎｉ（Ⅱ）和ｚｎ（Ⅱ）配合物在ＤＭＦ介质中的电化学行为。测得其电子转移过程的半波电位、标准速率常数及在ＤＭＦ中的扩散系数。并研究了吡啶轴向配位对Ｃｏ（Ⅱ）ＴＰ（ｏ－ＮＯ＿２）ＴＢＰ的氧化还原电位和速率的影响。提出了标题配位化合物在ＤＭＦ一吡啶混合溶剂中的电子转移机理。