Programmable Arrangement of Heterometal Ions in a Supramolecular Array of Porphyrin and Phthalocyanine

Abstract

Abstract Cofacial dimers of porphyrin and/or phthalocyanine are plausible frameworks for functional molecular systems such as molecular catalysts and molecular memories. We recently developed a supramolecular array of a porphyrin and phthalocyanine linked by a four-fold rotaxane. In this study, we demonstrated programmable hetero-ion arrangement in the heterodimer of these tetrapyrrolic ligands. Ni(II) and Fe(II) ions showed kinetically selective binding to the porphyrin, whereas Mn(II) ions selectively bound to the phthalocyanine, in the supramolecular array. After the first metal complexation, subsequent metal insertion into the vacant ligand afforded the programmed heterodinuclear complex. Moreover, the metal arrays were extended to heterotrinuclear complexes via ionic pairing of the cationic four-fold rotaxane with a tetraanionic metalloporphyrin.