四苯基钴卟啉化合物催化过亚硝酸根分解的研究

利用紫外-可见分光光度计在乙醇介质中研究了合成的4种对位取代四苯基钴卟啉对过亚硝酸根分解的催化作用. 首次发现钴卟啉可以催化ONOO^－分解, 且对位带吸电子基团的钴卟啉比对位带供电子基团的钴卟啉催化活性高. TPPCoCl, T(p-CH₃)PPCoCl, T(p-OCH₃)PPCoCl和T(p-Cl)PPCoCl在乙醇中的k_cat分别为1.69×10², 1.52×10², 1.43×10²和1.20×10³ mol^－1•L•s^－1. 动力学曲线和时间分辨谱证明这些钴卟啉是通过形成中间体催化过亚硝酸根分解的.     

卟啉化合物的研究——ⅩⅤ.双卟啉的合成及其与钴离子的络合反应

将双卟啉化合物作为“合成反应中心”是人工光合作用研究中很活跃的一个领域。困难的是,人们还不知道怎样排布两个卟啉环,分子才具有最有效传递电子和能量的构象。本文按下列反应合成了一个以柔性链连接的双卟啉化合物(3),以期当分子中络合金属后,籍助两个金属的协同作用和链的可塑性,达到在光反应过程中取最佳构象的目的(见图1)。化合物(1)按文献[1]合成。2、3尚未见报道,它们的结构,经元素分析及波谱分析确认。本文还研究了3与Co~(2 )络合反应的动力     

An ab initio analysis of the electronic structure and harmonic frequencies of nickel porphyrin

Ab initio calculations are performed to understand the geometry, electronic structure, and vibrational frequencies of nickel porphyrin (NiP). Hartree-Fock (HF) and second-order perturbation (MP2) theories are applied with polarized basis sets. The calculated geometrical parameters are in very good agreement with the crystal structure determination. The electronic structure and bonding are analyzed in terms of complexation and correlation effects. Not unexpectedly, the HF depiction of the metal-porphyrin interaction is rather ionic while ligand σ donation is dominant at the MP2 level. Scaled HF frequencies of NiP and its isotopomers are in very good agreement with observed infrared and resonance Raman data. Received: 7 January 1997 / Accepted: 6 May 1997     

Self-Assembly and X-Ray Crystal Structures of Novel Sn(IV)Porphyrin Phenolates

A series of complexes of the type [Sn(TTP)L₂] have been prepared by the condensation of [Sn(TTP)OH₂] (TTP = meso-tetratolylporphyrin) with a range of substituted phenols. The resulting complexes were characterised using ¹H NMR and single crystal X-ray diffraction techniques. In each case, the condensation of the phenols with the Sn(IV)porphyrin in CDCl₃ solution is slow (h) but essentially quantitative. The slow kinetics of the formation of the diaxial phenolate complexes allows for the identification, by ¹H NMR spectroscopy, of three independent complexes within this process, namely an outer-sphere (H-bonded) complex as well as two independent phenolate complexes. The rate of condensation is in the order phenol 4-methoxyphenol > 4-nitrophenol and suggests a steric rather than pKa dependency.     

Adduct of magnesium tetraphenylporphyrin with aniline for colorimetric detection of SO2

Adduct of magnesium tetraphenylporphyrin（MgTPP） with aniline for colorimetric detection of SO₂ was investigated in CH₂C1₂ by steady-state fluorescence and UV-vis absorption spectroscopic techniques.The UV-vis spectra showed that the increasing aniline concentrations resulted in red shift of 3 nm for MgTPP Soret absorption band.Once introduced,SO₂ competes with MgTPP for aniline,which eventually leads to the release of MgTPP and changes in the solution color/absorption.The fluorescence spectra suggested that MgTPP interacted with aniline to form 1:1 molecular adducts,and showed that the binding of MgTPP with aniline with the binding constants of 1.58-1.64 is not only endothermal but entropy-driven withΔH = 1.622 kJ mol^-1, AS = 9.389 J mor^-1 K^-1,and AG = -1.585 kJ mol^-1 at T= 298.15 K.     

单链四苯酚基卟啉在CTAB胶束微环境中的去质子化现象

叶绿素分子的光能转化功能的实现与其聚集状态、所处微环境性质及条件密切相关[1,2]．如何设计控制叶琳类分子在膜介质中的增溶位置，对于研究叶琳在膜体系中的跨膜电子传递、光能转化过程具有重要意义．本文研究了长链双亲卟啉──单链四苯酚基叶琳THPPH2在CTAB胶束中的去质子化，该过程能控制叶琳环在胶束中的增溶位置，使其由内核转移到胶束表面．1实验部分1·1仪器和测试条件岛津UV－240型紫外可见光谱仪（带有恒温夹套），狭缝宽2nm，石英池厚1cm，所用试剂皆为分析纯．UV光谱测试均在恒温条件下进行．1．2溶液的配制含一个十六…     

卟啉类化合物分子光电器件研究进展

分子电子器件是未来分子电路的微电子元件,已成为有机功能纳米材料研究的热点。 卟啉类化合物的π共轭体系表现出的独特光电性能和良好的热稳定性,使其作为光电器件、模拟生物酶、分子识别和传感材料在材料化学、医学、生物化学和分析化学等领域展现出良好的应用前景,由于卟啉分子平面结构的易修饰性,常用卟啉化合物组装单元来构建功能化的卟啉光电器件。 本文综述了卟啉类化合物的特点及其在光电器件中的应用进展。