Synthesis Inquiry And Properties Of Sandwich-type Phthalocyanine And Porphyrin-tetraazamacrocyclic Metal Complexes

Porphyrin and phthalocyanine compounds are macrocyclic compounds with highly conjugated systems, there high degree of stability and unique optical, electrical, magnetic properties has been attracting people to study. The macrocyclic ligands are pulled to a short distance by rare earth metal ions in the sandwich-type rare earth complexes of porphrin/pththalocyanine molecule, therefore, they shows a great potential as new molecular conductor, nonlinear optical materials and liquid crystal material etc.First of all, a series of thirteen phenylthio substituted sandwich rare earth complexes M[2,3-Pc（SPh）₈]₂（M =Y, Ce,…Lu, except for Pm, Tm） have been synthesized and the UV-vis and IR absorption spectra have been described systematically. The UV-vis and IR absorption show that all the metal ions in the complexes M[2,3-Pc（SPh）₈]₂ exist in the form of trivalence except the Ce ions which is exit the form of tetravalence. In addition, The Soret band and Q band of UV-vis absorption and the typical characteristic absorption peak of [Pc（SPh）8]·ˉ(ca. 1319^-1325 cm^-1) show a blue shift as the metal ionic radius reduce, which means with the dicrease of the size of metal ion, the conjugation（π-π interaction） between the rings become stronger.In the second part, 1,4,7,10-Tetraazacyclododecane was synthesized via amide acetal method and the purification step was optimized. Then, rare earth tetraphenylporphyrin was synthesized. After that, an exploratory study of sandwich-type porphyrin- tetraazamacrocyclic was trying.