Ditopic macropolycyclic complexes: synthesis of hybrid phthalocyaninoclathrochelates

Inorg Chem. 2005 Feb 21;44(4):822-4. doi: 10.1021/ic048189t.

Abstract

A remetalation (a capping group exchange) reaction of the boronantimony-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 Fe+/Fe2+ couples of macrobicyclic fragments and to phthalocyanine macrocycles.