Synthesis and Reductive Aromatization of Perfluoro Nickel Phthalocyanine Precursor Having Two Methoxy Groups on Adjacent Pyrrole Rings

Abstract Methanol‐mediated tetramerization of 3,4,5,6‐tetrafluorophthalonitrile with nickel(II) chloride yielded the perfluoro nickel phthalocyanine (NiPcF 16 ) derivative adj ‐(MeO) 2 NiPcF 16 , in which two methoxy groups are bound to adjacent pyrrole rings in an 18π‐electron backbone, together with opp ‐(MeO) 2 NiPcF 16 as a minor product, in which two methoxy groups are in diagonal position. The NiPcF 16 derivative adj ‐(MeO) 2 NiPcF 16 dissolved in organic solvents was converted to NiPcF 16 by electrochemical reduction, chemical reduction, or thermal conversion. A transparent glass electrode coated with an H ‐aggregate of NiPcF 16 was successfully prepared by utilizing electrochemical reduction. Whereas thermal conversion of adj ‐(MeO) 2 NiPcF 16 was inefficient, the tin(II)‐mediated reduction quantitatively afforded the corresponding NiPcF 16 , indicating that this mild transformation provides a practical method for converting alkoxylated precursors into the corresponding metallophthalocyanines.