Ditopic Macropolycyclic Complexes: Synthesis of Hybrid Phthalocyaninoclathrochelates

A remetalation (a capping group exchange) reaction of the boron−antimony-capped iron(II) clathrochelates with zirconium and
hafnium(IV) phthalocyanines in CH2Cl2/CH3OH medium afforded
the hybrid phthalocyaninoclathrochelates in a practically quantitative
yield. The complexes obtained have been characterized both on
the basis of elemental analysis, PD mass spectrometry, IR, UV−vis, 57Fe Mössbauer, and NMR spectroscopies, and crystallographically. An encapsulated iron(II) ion in an intermediate between
a trigonal-prismatic and a trigonal-antiprismatic environment of six
nitrogen atoms of the macrobicyclic ligand was found to be in a
low-spin state. The cyclic voltammograms show irreversible
oxidation and reduction waves assignable to Fe3+/Fe2+ couples of
macrobicyclic fragments and to phthalocyanine macrocycles.