Coexistence of Metal Phthalocyanine and Fullerene C60 Anions in Mixed {cryptand[2.2.2](Na+)}x(MPc)-x-1•(C60) - Salts (M = CoI, VIVO, x=2 and 1.5)

Salts containing metal phthalocyanine and fullerene anions: {cryptand[2.2.2](Na+)}(1.5){Co-I(Pc2-)}(-)(0.5)(C-60(center dot-))center dot 2C(6)H(4)Cl(2) (1) and {cryptand[2.2.2](Na+)}(2){(VO)-O-IV(Pc center dot 3-)}(-)(C-60(-))center dot C6H4Cl2 (2) were obtained. The {Co-I(Pc2-)}(-)anions are formed by metal centered reduction whereas the Pc2- macrocycles are reduced at the formation of {(VO)-O-IV(Pc center dot 3-)}(-). Fullerenes form zigzag chains in 1 in which they are positionally disordered showing different degree of dimerization [loose packed or pi-stacked pairs from the monomers and singly bonded (C-60(-))(2) dimers]. Singly bonded (C-60(-))(2) dimers in 2 also coexist with pairs of pi-stacked C(60)(center dot-)monomers. The (MPc)(-) anions are isolated in the salts alternating with the {cryptand(Na+)} cations. Magnetic measurements by EPR technique show the presence of spins in 1 both on C-60(center dot-)(S = 1/2) and the Co-I atoms having S = 1 spin state. These spins are weakly antiferromagnetically coupled in the fullerene chains (Theta = -6 K) but show nearly paramagnetic behaviour for isolated {Co-I(Pc2-)}(-) anions. Both S = 1/2 spins in 2 are mainly localized on V-IV and delocalized over Pc center dot 3- since only about 10 % of C-60(center dot-) from total amount of fullerene is preserved. Spins in 2 show only weak antiferromagnetic coupling with Theta = -2 K within one {(VO)-O-IV(Pc center dot 3-)}(-) unit.