Reaction of tin(iv) phthalocyanine dichloride with decamethylmetallocenes (M = Cr and Co). Strong magnetic coupling of spins in (Cp*Co){SnCl(Pc˙)}˙·2CHCl.

The reaction of tin(iv) phthalocyanine dichloride {SnCl(Pc)} with decamethylmetallocenes (CpM, M = Co, Cr) has been studied. Decamethylcobaltocene reduces SnCl(Pc) to form the (CpCo){SnCl(Pc˙)}˙·2CHCl (1) complex. The negative charge of {SnCl(Pc˙)}˙ is delocalized over the Pc macrocycle providing the alternation of the C-N(imine) bonds, the appearance of new bands in the NIR range and a strong blue shift of both the Soret and Q-bands in the spectrum of 1. The magnetic moment of 1 is equal to 1.68μ at 300 K, indicating the contribution of one S = 1/2 spin of the Pc˙ macrocycles. These macrocycles form closely packed double stacks in 1 with effective π-π interactions providing strong antiferromagnetic coupling of spins at a Weiss temperature of -80 K. Decamethylchromocene initially also reduces SnCl(Pc) to form the [(CpCr){SnCl(Pc˙)}˙ complex but further reaction between the ions is observed. This reaction is accompanied by the substitution of one Cp ligand of CpCr by chloride anions originating from {SnCl(Pc˙)}˙ to form the complex {(CpCrCl)(Sn(μ-Cl)(Pc))}·CHCl (2) in which the (CpCrCl) and {Sn(Pc)} species are bonded through the μ-bridged Cl anion. According to the DFT calculations, this reaction proceeds via an intermediate [(CpCrCl)(SnClPc)] complex.