Porphyrazines as molecular scaffolds: Flexible syntheses of novel multimetallic complexes

Reductive deselenation of selenodiazole-fused porphyrazines, followed by acylation of the resultant labile porphyrazinediamines, was used to prepare macrocycles bearing two Collins ligands, two oxamido residues, or two quinoline-2-carboxamido units. Peripheral coordination of copper(II) to the di-(quinoline-2-carboxamido)porphyrazine gave a metal-linked face-to-face porphyrazine dimer array. Sequential derivatization of the two amino groups in the porphyrazinediamines was used to prepare mixed peripheral ligand systems including a dimetallic picolinamido-Schiff base porphyrazine. Such systems exhibit strong metal-metal spin coupling and are anticipated to be of value in the synthesis of novel electronic and magnetic materials.