COORDINATION CHEMISTRY AND ELECTROCHEMISTRY OF LAYERED MOLECULAR SYSTEMS MADE OF PORPHYRINS WITH DIFFERENT REDOX PROPERTIES.

二聚卟啉作为多电子氧化还原体系的结构单元已引起人们的广泛关注。通过有机化学和配位化学的方法，两个卟啉分别通过卟啉外围取代基之间的共价键或中心金属之间的配位键连接起来。由于结构因素，如环间距和两个卟啉平面之间的取向对多电子氧化还原功能有很大的影响，本工作旨在创建新的双卟啉骨架。主要研究成果如下：(1)通过钴(III)卟啉与乙炔的一步反应，我们发现两个卟啉的吡咯氮S之间可以形成反常的(CH=CH-N，N‘)-键。我们建立了各种卟啉在该偶联反应中组合的实验条件和产率。(2)合成了多种锌、铜、钴混合双核配合物，并测定了它们的光谱性质和X射线晶体结构。(3)我们发现与锌、铜、钴、铁等金属配位的异常三、四配位卟啉很容易合成。尤其是，Fe-O-Fe键很容易构建成混合金属四氢卟啉。吡咯氮基之间具有不寻常间隔基的双卟啉已被证明是分层卟啉体系的构建块。

Dimeric porphyrins have been drawing much attention as structural units for multi-electron redox systems. Two porphyrins are linked by covalent bonding between substituents at the porphyrin periphery or by ligand bonding between central metals, as approaches by organic chemistry and coordination chemistry, respectively. Since structural factors such as inter-ring distance and orientation between two porphyrin plane make great influence on the multi-electron redox functions, this work was intended to create new bisporphyrin framework. The research achievements are as following.(1) We had already found that unusual (CH=CH-N,N')-link can be made between pyrrole nitrogen s of two porphyrins by one-step reaction between Co(III) porphyrin and acetylene. We have established experimental conditions and yields for combinations of various porphyrins in this coupling reaction. (2) We have prepared various mixed binuclear complexes of bisporphyrin with combinations of Zn, Cu, and Co in good yields and determined their spectroscopic properties and X-ray crystal structure. (3) We have shown that unusual tris- and tetrakis-porphyrins metallated with Zn, Cu, Co, and Fe are easily synthesized. In particular, a Fe-O-Fe link was readily constructed to lead to mixed-metal tetrakisporphyrins.The bisporphyrins with unusual spacers between pyrrole nitrogens have been shown to be useful as the building block for layered porphyrin systems.