Synthesis And Properties Of Porphyrinoids

Porphyrin is a kind of π-conjugated system which can be easily modified. The approaches of modification including meso- or β-substitution, core-modification, metal coordination, changing the connection style between the pyrrole subunit, embedding with new functional building blocks and contracting or expanding the conjugated system. The porphyrin analogues obtained by changing the porphyrin ring structure are called porphyrinoids. With the depth of the porphyrin research, porphyrinoid fields have also developed rapidly. Porphyrinoids own the general characteristics of the common porphyrin. However, due to the changes in the core structure, they have also obtained the novel and interesting properties, such as stabilization of special valent metal, ion recognition, novel aromaticity, special optical properties and so on, that different from the porphyrins. Therefore, they have great values in application.Corrole and porphycene are the two novel porphyrinoids obtained by changing the connection style of porphyrin. In order to get the corrole with a large red shift in absorption spectrum, we have designed the corrole according to a ring fusion method. Then, the structure and optical properties are studied. We think this is a good supplication for exploring the application of corroles. Porphycene has novel structure and optical properties compared with porphyrin. There are only a few researches involve the metal coordination of porphycenes, so in this dissertation we have tried to synthesize several porphycene metal compounds with the modified methods. The structure and optical properties are studied, also, we try to find their potential application in other fields.Introduction of novel building blocks in the porphyrin system has been an important means in the porphyrinoid synthesis. Thienopyrrole is a special building block. In the dissertation, we get two novel porphyrinoid by using this subunit.The major results are summarized as follows:1. Several building blocks have been prepared by using the commonly introduced reaction. Their structures have been characterized with 1H-NMR spectra.2. The benzene ring fused corrole metal coordination has been prepared by using a template method. The structure has been certified by the X-ray diffractometer. The strongest absorption peak is significantly red-shifted in about 50 nm. We have also synthesized two metal coordination of corrole to certify the unique properties of the stabilization on the high valence metal ions.3. Two porphycene metal coordinations have been prepared by the improved method. The sizes of the metal ions have great influence on the structure of these metal coordinatons. From their UV-vis spectra, we can find that the planar structure always result in a strong absorption. We have also study the porphyrcene-P complex, and we find that the introduction of phosphorus greatly enhanced the fluorescence property of porphycene.4. The thienopyrrole subunit was successfully introduce into the porphyrin system by using the classic’3+1’methodology. This porphyrinoid has unique aromaticity. Intriguingly, it was found to be a very stable and planar 20-π macrocycle in distinct contrast to the 18-π aromatic tetrapyrrolic porphyrin. The reduction radical compound can be achieved by chemistry or electrochemistry method. Besides, we have synthesized a 30π expanded porphyrin embedded with two thienopyrrole building blocks by using the Macdonald-type condensation reaction. This compound has a rigid structure and because of the conjugated expansion effect, the UV-vis spectra is significantly red-shifted to near 600 nm for B band and 1200 nm for Q band. It appears to be a tunable NIR dyes...