We present the review of fundamental parameters and properties of metalloporphyrins/
phthalocyanines with axial covalent M–O/M–N bonds (M is a
metal atom in the oxidation degree more than 2+) for use in the development
of the chemistry of molecular materials. The porphyrin complexes covalently
bonded along the axial axis are differed by the high oxidation state of a metal
atom and related heightened axial reactivity compared with the corresponding
derivatives of two charged metal cations, applications of which in both scientific
studies and practical areas are most widely reflected in publications. The
selection of chemical structures of the 3d, 4d, 5d, and 4f metal derivatives of
porphyrins/phthalocyanines and study of their properties promising in the
detection of bioactive organic bases, optoelectronics (active components of allsmall
molecular organic solar cells), and spintronics (room-temperature magnetocaloric
materials) are detailed in the article. The results of the first critical
analysis of this topic in the review and the insight into chemical structure
effects in the function of MPXs/MPcXs as molecular materials will contribute
to further development of their organometallic chemistry.
