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{CoI(Pc2–)}–0.5(C60·–)·2C6H4Cl2 (1) and {cryptand[2.2.2](Na+)}2{VIVO(Pc·3–)}–(C60–)·C6H4Cl2 (2) were obtained. The {CoI(Pc2–)}–anions are formed by metal centered reduction whereas the Pc2– macrocycles are reduced at the formation of {VIVO(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 (C60–)2 dimers]. Singly bonded (C60–)2 dimers in 2 also coexist with pairs of π‐stacked C60·–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 C60·–(S = 1/2) and the CoI 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 {CoI(Pc2–)}– anions. Both S = 1/2 spins in 2 are mainly localized on VIV and delocalized over Pc·3– since only about 10 % of C60·– from total amount of fullerene is preserved. Spins in 2 show only weak antiferromagnetic coupling with Θ = –2 K within one {VIVO(Pc·3–)}– unit. Salts containing metal phthalocyanine and fullerene anions were obtained. Fullerenes form zigzag chains in 1 in which they are positionally disordered and show different degrees of dimerization. Magnetic coupling is observed only in the fullerene subsystem, whereas paramagnetic metal phthalocyanine anions are magnetically isolated and do not show essential magnetic coupling with the fullerene subsystem.