Syntheses and Characterization of Copper Complexes of Tetraphenyl-m-benziporphyrin、Thia-p-benziporphyrin and Sulfur Containing Expanding Porphyrin

• Main Authors: Cheng-Yu Lin, 林貞佑
• Other Authors: Chen-Hsiung Hung
• Format: Others
• Language: zh-TW
• Published: 2005
• Online Access: http://ndltd.ncl.edu.tw/handle/54772272694071962684

碩士 === 國立彰化師範大學 === 化學系 === 93 === Carbaporphyrin has at least one of the internal nitrogens replaced with a carbon. Recent studies show that carbaporphyrin has distinct physical and chemical properties comparing to a regular porphyrin. Importantly, the carbaporphyrin has an internal carbon which can be used to form organometallic metal-carbon bond. The members of the carbaporphyrin family are continuously increasing. Recently we have synthesized novel core-modified benziporphyrin from the condensation of 1,4-bis(α-hydroxyl-benzyl)-benzene with 5,10-ditolyl-16-thia- 5,10,15,17-tetra-hydrotripyrrin using BF3•OEt2 as catalyst following with a DDQ oxidation. We have also prepared the copper complexes of tetraphenyl- benziporphyrin (TPBP). The copper complex is a tetranuclear complex with [Cu2Cl4]2- unit bridging between two Cu(ClTPBP)-. The substitution of internal phenylene proton of TPBP with a chloride represents the first metal assisted chlorination on TPBP complexes. The expanded porphyrins constituting from five pyrrole rings to as many as twelve pyrrole rings exhibit different physical properties and solid state structures. With low yields, the chemistry of expanded porphyrin develops rapidly in recent years because expanded porphyrins are synthesized by a relatively simple methodology from commonly accessible substrates which creates an opportunity for further extensive studies on the coordination chemistry and anion-binding properties. We are focusing on the prepation of heteroatom substituted hexaphyrins. We have already reported the preparation of N3S3-trithiahexaphyrin. The acid-catalyzed condensation of pyrrole and 2,5-bis（2,6-dichlorophenylhydroxymethyl）thiophene yields, apart from the well known dithiaporphyrin and N3S3-trithiahexaphyrin, N4S4- octaphyrin. The mass spectrometry of N4S4-octaphyrin is isolated suggests empirical formula of C88H42N4S4Cl16. The crystal structure of free base N4S4-octaphyrin indicates that N4S4-octaphyrin possess helical figure-eight geometry. The protonation mechanism reflects the unusual structure of the molecule. We have obtained saddle form 、a non-planar form and a planar crystal structures