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

Methanol‐mediated tetramerization of 3,4,5,6‐tetrafluorophthalonitrile with nickel(II) chloride yielded the perfluoro nickel phthalocyanine (NiPcF16) derivative adj‐(MeO)2NiPcF16, in which two methoxy groups are bound to adjacent pyrrole rings in an 18π‐electron backbone, together with opp‐(MeO)2NiPcF16 as a minor product, in which two methoxy groups are in diagonal position. The NiPcF16 derivative adj‑(MeO)2NiPcF16 dissolved in organic solvents was converted to NiPcF16 by electrochemical reduction, chemical reduction, or thermal conversion. A transparent glass electrode coated with an H‐aggregate of NiPcF16 was successfully prepared by utilizing electrochemical reduction. While thermal conversion of adj‐(MeO)2NiPcF16 was inefficient, the tin(II)‐mediated reduction quantitatively afforded the corresponding NiPcF16, indicating that this mild transformation provides a practical method for converting alkoxylated precursors into the corresponding metallophthalocyanines.