Coexistence of Metal Phthalocyanine and Fullerene C 60 Anions in Mixed {cryptand[2.2.2](Na + )} x (MPc) – x ‐1 ·(C 60 ) – Salts (M = Co I , V IV O, x = 2 and 1.5)

Salts containing metal phthalocyanine and fullerene anions: {cryptand[2.2.2](Na + )} 1.5 {Co I (Pc 2– )} – 0.5 (C 60 · – ) · 2C 6 H 4 Cl 2 ( 1 ) and {cryptand[2.2.2](Na + )} 2 {V IV O(Pc · 3– )} – (C 60 – ) · C 6 H 4 Cl 2 ( 2 ) were obtained. The {Co I (Pc 2– )} – anions are formed by metal centered reduction whereas the Pc 2– macrocycles are reduced at the formation of {V IV O(Pc · 3– )} – . Fullerenes form zigzag chains in 1 in which they are positionally disordered showing different degree of dimerization [loose packed or π‐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 π‐stacked C 60 · – 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 · – ( S = 1/2) and the Co I atoms having S = 1 spin state. These spins are weakly antiferromagnetically coupled in the fullerene chains (Θ = –6 K) but show nearly paramagnetic behaviour for isolated {Co I (Pc 2– )} – anions. Both S = 1/2 spins in 2 are mainly localized on V IV and delocalized over Pc · 3– since only about 10 % of C 60 · – from total amount of fullerene is preserved. Spins in 2 show only weak antiferromagnetic coupling with Θ = –2 K within one {V IV O(Pc · 3– )} – unit.