Multistep synthesis and X-ray structures of carboxyl-terminated hybrid iron(II) phthalocyaninatoclathrochelates and their postsynthetic transformation into polytopic carboranyl-containing derivatives.

A multistep general synthetic strategy towards polytopic carboranyl-containing (semi)clathrochelate metal complexes, based on the template synthesis, transmetallation, amide condensation and 1,3-dipolar cycloaddition reactions, is developed. Their mono(semi)clathrochelate precursors with a single reactive group were obtained using a transmetallation of the triethylantimony-capped macrobicyclic precursor. The thus obtained carboxyl-terminated iron(II) semiclathrochelate underwent a macrobicyclization with zirconium(IV) phthalocyaninate to form the corresponding phthalocyaninatoclathrochelate. The direct one-pot template condensation of the suitable chelating and cross-linking ligand synthons on the Fe2+ ion as a matrix was also used for its preparation. Further amide condensation of the aforementioned semiclathrochelate and hybrid complexes with propargylamine in the presence of carbonyldiimidazole gave the (pseudo)cage derivatives with a terminal CC bond. Their "click" reaction with an appropriate carboranylmethyl azide afforded the ditopic carboranosemiclathrochelates and the tritopic carboranyl-containing phthalocyaninatoclathrochelates with a flexible spacer fragment between their polyhedral entities. The obtained new complexes were characterized using elemental analysis, MALDI-TOF mass spectrometry, multinuclear NMR, and UV-vis spectroscopy, and by single crystal X-ray diffraction experiments. Their FeN6-coordination polyhedra show a truncated trigonal-pyramidal geometry, while the cross-linking heptacoordinate Zr4+ or Hf4+ cations in the hybrid compounds form the MIVN4O3-coordination polyhedra with the geometry of a capped trigonal prism.