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 CH 2 Cl 2 /CH 3 OH 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, 5 7 Fe Mossbauer, 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 Fe 3 + /Fe 2 + couples of macrobicyclic fragments and to phthalocyanine macrocycles.