Development of Novel Tetrapyrrole Ligands and Their Metal Complexes with New Functions

四吡咯骨架大环结构由于其独特的结构和功能而备受关注。本研究合成了卟啉的结构异构体二茂卟啉和半二茂卟啉。通过X射线晶体分析确定每个结构。研究了这些配体与各种过渡金属的配合物，特别是其铁钴配合物的大环骨架取代效应。本文合成了一系列溴代卟啉配体的钴配合物，并用CV、UV-VIS和NMR研究了其性质。溴原子数与肌红蛋白的各种物理化学性质呈线性关系，以铁卟啉为人工辅基的重组肌红蛋白具有极高的分子氧亲和力和较低的自氧化速率。本研究表明，血红素骨架的修饰将是一种制备功能化血红素蛋白的有效方法。采用溶胶-凝胶法将疏水性的四吡咯色素维生素B12固定在不同的电极上。该络合物被物理地保留在形成于电极上的硅胶膜中。固定化的配合物表现出Co（II）/Co（I）氧化还原对，并保留其电化学活性。在-1.2Vvs.Ag/AgCl水溶液中，该电极对溴化苄进行了控制电位电解，得到了脱卤产物联苄和甲苯，1h总转化数超过1000。

Macrocyclic structure with tetrapyrrole skeleton is great interest because of its unique structure and function. In this study, porphycene and hemiporphycene which are structural isomers of porphyrin have been synthesized. Each structure was-determined by X-ray crystal analyses. These ligands complex with various transition metal, and especially substiution effect with macrocycle skeleton of its iron and cobalt complex was studied. The cobalt(II) complexes of a series of peripheral substituted porphycene ligands with bromine have been synthesized and its various properties have been investigated by means of CV,UV-VIS and NMR spectroscopies. Linear relationships between the number of bromine and various physicochemical properties were observed.Reconstituted myoglobin with iron porphycene as an artificial prosthetic group exhibits an extremely high molecular oxygen affinity and low autooxidation rate. This study showed that the modification of the heme framework will serve as an effective method for the creation of a unique functionalized hemoprotein.Hydrophobic vitamin B12 which is tetrapyrrole pigment was immobilized onto various electrode by a sol-gel reaction. The complex was physically retained in a silica gel film which is formed on an electrode. The immobilized complex exhibits the Co(II)/Co(I) redox couple and retain its electrochemical activity. This electroactive complex shows a high reactivity towards organic halides, and the controlled-potential electrolysis of benzyl bromide using the sol-gel modified electrode at -1.2 V vs. Ag/AgCl in aqueous solution afforded dehalogenated products, bibenzyl and toluene, with a total turnover number over 1000 for 1 hour.