Crystalline anionic salts with copper octafluoro- and hexadecafluorophthalocyanines, (Bu4N+)(2)[Cu-II(F8Pc)(4)](2)center dot 2C(6)H(4)Cl(2) (1) and (PPN+)(3)[CuF16Pc](3)(3)center dot 2C(6)H(5)CN (2), where PPN+ is bis(triphenylphosphoranylidene)ammonium and Pc is phthalocyanine, have been obtained. The absence of noticeable absorption in the NIR range and DFT calculations for 1 indicate that both negative charges are mainly localized on the Pc ligand, and that the [Cu-II(F8Pc)(4)](2) dianions are formed without reduction of CuII. The magnetic moment of 1.60 mu B corresponds to the contribution of one S = 1/2 spin per dianion. The spin is localized on the CuII atom, which shows an EPR signal characteristic of CuII. Dianions are isolated in 1, providing only weak magnetic coupling of spins with a Weiss temperature of -4 K. Salt 2 contains closely packed pp stacks built of [CuF16Pc]- anions of types I and II, and the interplanar distances are 3.187 and 3.275 angstrom. According to the DFT calculations, the [CuF16Pc]- anions of types I and II can have different charge distributions, with localization of an extra electron on the copper atoms to form diamagnetic [CuI(F16Pc)(2)]-monoanions or delocalization of an extra electron on the F16Pc ligand to form [CuII(F16Pc)center dot(3)](center dot) having an S = 1/2 (Cu-II) + 1/2 (F16Pc center dot(3)) spin state. In fact, at 300 K, the magnetic moment of 2 of 3.25 mu B per formula unit is rather close to the contribution from two [Cu-II(F16Pc)center dot(3)](center dot) (calculated mu eff is 3.46 mu B). The Weiss temperature of -21.5 K indicates antiferromagnetic coupling of spins, which can be modeled by stronger intermolecular coupling between (F16Pc)center dot(3) with J1/kB = -23.5 K and weaker intramolecular coupling between CuII and (F16Pc)center dot(3) with J2/kB = -8.1 K. This interaction is realized in the {[Cu-II(F16Pc)center dot(3)](center dot)}(2) dimers separated by diamagnetic [CuI(F16Pc)(2)](-) species. In spite of the stacking arrangement of phthalocyanine macrocycles in 2, the inhomogeneous charge distribution and nonuniform distances between the macrocycles should suppress electrical conductivity.