Perfluorinated porphyrazines. 3. Synthesis, spectral-luminescence and electrochemical properties of perfluorinated octaphenylporphyrazinatozinc(II)

Perfluorinated Porphyrazines. 5. Perfluoro-a,b-dicyanostylbene: Molecular Structure and Derived (Sub)Porphyrazine Complexes with IIIa Group Elements

“…The maxima of the Q-and Soret bands for macrocyclic complexes 2, 3 and 4 containing perfluorinated phenyl rings are shifted hypsochromically as compared to non-fluorinated species. A similar effect of perfluorination was observed in the case of In III and Zn II complexes [5,6] and was explained by stronger stabilization of HOMO than LUMO. The effect of perfluorination on the Q-band position correlates with electronegativity of the central coordinating atom and for the IIIa group elements is decreased in the order: B III (387 cm -1 ) > Al III (381 cm -1 ) > Ga III (302 cm -1 ) > In III (222 cm -1 ).…”

“…[5] Earlier it was shown that tedious chromatographic separation of cisand trans-isomers of 1 is a dispensable procedure and their mixture can be successfully used in template cyclotetramerization leading to formation of porphyrazine complexes [MPAF 40 ] (M = Mg II , Zn II and (X)In III ). [5,6] Non-fluorinated compounds -complexes of octaphenylporphyrazine, e.g.…”

“…In the spectra of non-fluorinated phenyl substituted macrocyclic complexes the intense charge transfer (CT) band from peripheral aryl groups to the central macrocycle is observed: Ar→subporphyrazine at ca. 400 nm [14,22] or Ph→porphyrazine at 450-480 nm [5,6] ). This CT band disappears when peripheral phenyl groups are perfluorinated and become strong electron-acceptors.…”

“…This CT band disappears when peripheral phenyl groups are perfluorinated and become strong electron-acceptors. In addition perfluorination increases the dihedral angles of aryl groups with pyrrole rings of macrocycle, [6] thus diminishing the p-interaction.…”

“…In a series of our works we have prepared octa(pentafluorophenyl)porphyrazine [H 2 PAF 40 ] and its complexes with Mg II , Zn II and In III and demonstrated the crucial role of perfluorination in regulation of acid-base properties of meso-and inner nitrogen atoms and in photophysical properties such as quantum yield of fluorescence and singlet oxygen generation. [5,6] In addition, the presence of fluorinated phenyl residues widens the opportunities for modification of periphery of the macrocycle by nucleophilic substitution of fluorine atom(s). Thus, S N Ar reaction was employed for preparation of butoxy and water soluble galactosyl derivatives from [ZnPAF 40 ], in which up to eight F-atoms in p-positions of phenyl rings can be substituted.…”