Novel Route to Functionalized Tetraaryltetra[2,3]naphthaloporphyrins via Oxidative Aromatization

A novel general route to substituted meso-tetraaryltetra[2,3]naphthaloporphyrins (Ar₄TNP) and meso-tetraaryloctamethoxytetra[2,3]naphthaloporphyrins (Ar₄(MeO)₈TNP) via oxidative aromatization of nonaromatically fused porphyrin precursors is described. Ar₄(MeO)₈TNPs exhibit more red-shifted absorption bands than Ar₄TNPs and differ dramatically in solubility. The first X-ray crystallographic structure of tetranaphthaloporphyrin, i.e., PdAr₄TNP (Ar = 4-MeO₂CC₆H₄), revealed that the degree of nonplanar distortion of this macrocycle is only slightly higher than that of the homologous tetrabenzoporphyrins (Ar₄TBP).