The Salts of Copper Octafluoro- and Hexadecafluorophthalocyanines Containing [Cu II (F 8 Pc) 4- ] 2- Dianions and [CuF 16 Pc] - Monoanions.

Crystalline anionic salts with copper octafluoro- and hexadecafluorophthalocyanines, (Bu4 N+ )2 [CuII (F8 Pc)4- ]2- ·2C6 H4 Cl2 (1) and (PPN+ )3 [CuF16 Pc]3 3- ·2C6 H5 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 [CuII (F8 Pc)4- ]2- dianions are formed without reduction of CuII . The magnetic moment of 1.60 μB 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 π-π stacks built of [CuF16 Pc]- anions of types I and II, and the interplanar distances are 3.187 and 3.275 Å. According to the DFT calculations, the [CuF16 Pc]- 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 (F16 Pc)2- ]- monoanions or delocalization of an extra electron on the F16 Pc ligand to form [CuII (F16 Pc)•3- ]•- having an S = 1/2 (CuII ) + 1/2 (F16 Pc•3- ) spin state. In fact, at 300 K, the magnetic moment of 2 of 3.25 μB per formula unit is rather close to the contribution from two [CuII (F16 Pc)•3- ]•- (calculated μeff is 3.46 μB ). The Weiss temperature of -21.5 K indicates antiferromagnetic coupling of spins, which can be modeled by stronger intermolecular coupling between (F16 Pc)•3- with J1 /kB = -23.5 K and weaker intramolecular coupling between CuII and (F16 Pc)•3- with J2 /kB = -8.1 K. This interaction is realized in the {[CuII (F16 Pc)•3- ]•- }2 dimers separated by diamagnetic [CuI (F16 Pc)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.