Salen-Capped Porphyrins as an Active Site Model of Metalloenzymes: Synthesis and Their Intramolecular Interactions between the Metal Complexes

Abstract
Reversible Schiff base condensation of bis(salicylaldehyde)-linked porphyrins and ethylenediamine under high dilution gave salen-capped porphyrins in high yields. Site selective insertion of nickel(II) into the salen and zinc(II) into the porphyrin gave the corresponding Ni–Zn heterobinuclear complexes. The geometrical relationship between the two metal centers was estimated by 1H NMR spectroscopy. The porphyrin π electronic state of these Ni-salen-capped Zn-porphyrins was perturbed by their Ni-salen cap, which was studied by 400 MHz 1H NMR, UV-Vis spectra, fluorescence, and cyclic voltammetry measurements.

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