Chiral Recognition Of Monoamines, Monoalcohols By Malonamide-linked Bisporphyrinates And Structural Characterization Of β, β’-linked Porphyrin-chlorin Heterodimers

This thesis is about the studies on porphyrin dimer or heterodimers.There are the following two parts. In the first part, we have synthesized malonamide-linked zinc bisporphyrinate [Zn1P] and obtained a single crystal of [Zn2P] based on our previous work. We have studied the chiral recognition of a various of chiral monoamines by using these two porphyrinates as hosts. Our results suggest that the signs of CD for the chiral amines of the same handedness with R as an aryl group are just opposite to those with R as an alkyl group. We have also studies the chiral recognition of chiral monoalcohols by these two porphyrinates, and investigated the chiral recognition mechanism by UV-vis and 1H NMR.In the second part, a series of β, β’-linked porphyrin-chlorin heterodimers and their metallic complexes have been synthesized and characterized by X-ray crystallography. In all the structures, the pyrroline group in chlorin moiety and the pyrrole group in porphyrin moiety are directly connected by a single bond. Pyrroline ring has two sp3 hybridized carbons. The direct bonding makes the pyrroline group and the pyrrole group have relative rigid conformation, showing a dihedral angle of ~ 70° between them. For nickel complexes, the chlorin planes show large saddling and moderate ruffling conformation. The C-H×××p interaction could contribute to the saddling conformation. Their UV-vis and fluorescence spectral data have also been briefly discussed.