新型不对称型金属卟啉的谱学性质及非线性光学性质研究

本文合成了几种新型吡啶基修饰的不对称卟啉和金属卟啉,并用核磁、质谱、元素分析、红外光谱、紫外-可见光谱等方法进行了表征,分子模拟研究得到了与光谱分析一致的结果。通过Z-扫描实验对卟啉配合物的非线性光学性质进行了详细研究,这些样品在激光作用下,在532 nm处显示出了强烈的非线性吸收,且取代基位置和金属的不同,均会对三阶非线性折射率的大小产生很大的影响。     

Nuclear magnetic resonance of paramagnetic metalloporphyrins

The present article reviews and discusses proton magnetic resonance studies on metalloporphyrins which provide good models for heme proteins in their physical and chemical properties. Emphasis is given on the discussion of the₁Hnmr work done in our laboratory.     

卟啉及其类似物超分子功能的分析应用

应用超分子化学的理论和研究成果解决分离、分析与有关理论问题是现代分析化学的一个重要方面。评述了卟啉及其金属配合物、类似物的分子识别、组装和仿生催化作用及其在生物相关物质的色谱分离分析，各类传感器、模拟酶分析等方面的应用研究进展，也展望了发展趋势。引用文献８６篇。     

Metalloporphyrin receptors for bases

The review summarizes data on the reversible addition of inorganic and organic biologically active bases at the coordination sites of mixed complexes containing the porphyrin dianion as one of ligands. An analysis of the thermodynamic parameters revealed new receptors for small cyclic molecules holding promise for analytical purposes and sensorics. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 636–654, April, 2007.     

高分子负载Mn（Ⅲ）卟啉／PhIO体系催化烯烃环氧化反应研究

研究了负载化金属卟啉催化烯烃环氧化反应的催化活性，探索了催化反应体系中轴向配体、溶剂、锰卟啉在高分子上的担载量及反应温度等对催化反应的影响．结果表明，金属卟啉负载化后，增大了催化剂的稳定性．本文还考察了负载化催化剂对苯乙烯催化环氧化反应的动力学行为，根据Ｍｉｃｈａｅｌｉｓ－Ｍｅｎｔｅｎ方程，求得了相关的动力学参数     

Encapsulation of an Ionic Metalloporphyrin into a Zeolite Imidazolate Framework in situ for CO2 Chemical Transformation via Host–Guest Synergistic Catalysis

It is a great challenge to rationally integrate multiple reactive sites into a composite material with confined nanospace, which can be applied as a nanoreactor to facilitate targeting catalytic reaction. In this work, an ionic metalloporphyrin has been encapsulated in situ into ZIF‐8 for a solvent‐free synthesis of cyclic carbonates from CO₂ and epoxides without any co‐catalyst under 1 atm CO₂.     

金属卟啉类模拟酶催化剂研究

对金属卟啉化合物在催化氧化反应中的应用和机理方面的最新研究成果进行了详细的阐述,并概述了量化计算方法在金属卟啉分子设计、结构及催化活性等方面的应用.也介绍了本课题组在上述领域的最新研究成果.预测了金属卟啉化合物在催化领域的应用前景.     

Supramolecular architectures of functionalized tetraphenylmetalloporphyrins in crystalline solids. Studies of the 4-methoxyphenyl, 4-hydroxyphenyl and 4-chlorophenyl derivatives

Abstract

A series of new ‘inclusion’ materials based on tetra-4-methoxyphenyl, tetra-4-hydroxyphenyl and tetra-4-chlorophenyl derivatives of the metalloporphyrin system, in combination with a wide variety of guest molecules and ligands, have been prepared, and their structural systematics analysed. Crystallographic investigations have confirmed that the supramolecular arrangement of the hydroxyphenylporphyrin species is dominated by interporphyrin directional hydrogen-bonding interactions, and consists of continuous networks of strongly coordinated entities with varying degrees of cross-linking and rigidity. Guest molecules can be absorbed in these solids in distinctly defined sites of the lattice: in the small interhost cages of fixed size between adjacent intercoordinated porphyrin hosts, or in extended one-dimensional channels formed between the hydrogen bonded host arrays running parallel or perpendicular to the porphyrin plane. For polar ligands with strong nucleophiles, their potential coordination to the metal center provides an additional recognition factor. The stacking mode (offset geometry or overlapping) of the host metalloporphyrin arrays is also affected by the nature of the incorporated guest/ligand. Materials based on the chloro-substituted porphyrins were found to form similarly networked structural modes, influenced by the molecular shape as well as by halogen-halogen noncovalent interactions. Formation of a polar tubular intermolecular architecture capable of aligning organic dipolar guest molecule in the crystal bulk has also been demonstrated. The methoxy-substituted materials form clathrate-type structures characterized by dense layered arrangement of the porphyrin building blocks in two-dimensions. The various structural features directing the observed modes of the supramolecular architecture, and affecting the host structure as well as the guest mobility in it, are discussed.