Three new tripyridyl tripodal ligands appended with either fullerene or pyromellitdiimide moieties, named C-60-s-Tripod, C-60-l-Tripod, and PI Tripod, were synthesized and introduced into a porphyrin macroring N-(1-Zn)(3) (where 1-Zn = trisporphyrinatozinc(II)). From UV-vis absorption and fluorescence titration data, the bindin constants of C-60-s-Tripod, C-60-l-Tripod, and PI-Tripod with N-(1-Zn)(3) in benzonitrile were estimated to be 3 X 10(8), 1 X 10(7), and 2 x 10(7) M-1, respectively. These large binding constants denote multiple interactions of the ligands to N-(1-Zn)(3). The binding constants of the longer ligand (C-60-l-Tripod) and the pyromellitdiimide ligand (PI-Tripod) are almost the same as those without the fullerene or pyromellitdiimide groups, indicating that they interact via three pyridyl groups to the porphyrinatozinc(II) coordination. In contrast, the larger binding constants and the almost complete fluorescence quenching in the case of the shorter ligand (C-60-s-Tripod) indicate that the interaction with N-(1-Zn)(3) is via two pyridyl groups to the porphyrinatozinc(II) coordination and a pi-pi interaction of the fullerene to the porphyrin(s). The fluorescence of N-(1-Zn)(3) was quenched by up to 80% by the interaction of C-60-l-Tripod. The nanosecond transient absorption spectra showed only the excited triplet peak of the fullerene on selective excitation of the macrocyclic porphyrins, indicating that energy transfer from the excited N-(1-Zn)(3) group to the fullerenyl moiety occurs in the C-60-l-Tripod/N-(1-Zn)(3) composite. In the case of PI-Tripod, the fluorescence of N-(1-Zn)(3) was quenched by 45%. It seems that the fluorescence quenching probably originates from electron transfer from the excited N-(1-Zn)(3) group to the pyromellitdiimide moiety.