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In the title compound, C33H25N2+·PF6−, the naphthalene ring system is twisted with respect to the anthracene and benzene rings, making dihedral angles of 72.40 (3) and 71.39 (4)°, respectively. The crystal structure is stabilized by intermolecular C—H...F hydrogen bonding. Four F atoms of the hexafluorophosphate anion are disordered over two sets of sites in a 0.645 (4):0.355 (4) ratio.