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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.

The reaction with sodium cyanide of the μ-oxo-bridged complex of tetra-4-tert-butyl-substituted iron phthalocyanine (form ‘690’) and that of the product of its treatment with organic bases such as Py, Im, etc. (form ‘627’) result in the formation of the same ferrous bis-cyanide complex Na 2[ Pc t Fe II ( CN )2] which can be readily oxidized to the analogous ferric complex Na [ Pc t Fe III ( CN )2]. Form ‘690’ has been oxidized to the corresponding ferric μ-oxo complex (form ‘630’). Data for all μ-oxo-bridged complexes (chemical behavior; electronic, NMR, Mössbauer, X-ray photoelectron and ESR spectra; magnetic susceptibility) are discussed, and based on them, the following structures are proposed: ( HPc t Fe II )2 O (form ‘690’), H 2[( LPc t Fe II )2 O ] (form ‘627’) and ( Pc t Fe III )2 O (form ‘630’).

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