Synthesis and properties of fullerene (C₇₀) complexes of 2,6-bis(porphyrin)-substituted pyrazine derivatives bound to a Pd(II) ion

2,6-Bis(porphyrin)-substituted 3,5-dimethylpyrazine and its zinc complex bound C₇₀ to yield 1:1 inclusion complexes, which were characterised by ESI-MS, UV-vis, fluorescence and NMR spectroscopies. Association constants of the C₇₀ complexes were determined by fluorescence and NMR spectral analyses. A decrease in absorbance of the Soret band of the pyrazine derivative by the effect of C₇₀ was observed, suggesting the existence of a charge transfer interaction between C₇₀ and porphyrin. Experimentally reliable values for the association constants were obtained by the NMR method and were about six times larger than those of the corresponding C60 complexes. Palladium complexation of the porphyrin-pyrazine ligand was found to enhance the association with fullerene. The association constant of 2,6-bis(porphyrin-Zn)- substituted 3,5-dimethylpyrazine-Pd(II) complex with C₇₀ was determined to be 8400±900M^-1. From the comparison of the association constants, it was found that inclusion room for C₇₀ in the Pd(II) complex was maintained, juxtaposed between porphyrins attached to the opposite sides of the pyrazine ligands.