Reaction of tin(iv) phthalocyanine dichloride with decamethylmetallocenes (M = CrII and CoII). Strong magnetic coupling of spins in (Cp*2Co+){SnIVCl2(Pc˙3-)}˙-·2C6H4Cl2.

Author(s) Konarev, D.V.; Troyanov, S.I.; Shestakov, A.F.; Yudanova, E.I.; Otsuka, A.; Yamochi, H.; Kitagawa, H.; Lyubovskaya, R.N.
Journal Dalton Trans
Date Published 2018 Jan 23

The reaction of tin(iv) phthalocyanine dichloride {SnIVCl2(Pc2-)} with decamethylmetallocenes (Cp*2M, M = Co, Cr) has been studied. Decamethylcobaltocene reduces SnIVCl2(Pc2-) to form the (Cp*2Co+){SnIVCl2(Pc˙3-)}˙-·2C6H4Cl2 (1) complex. The negative charge of {SnIVCl2(Pc˙3-)}˙- 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 1.68μB at 300 K, indicating the contribution of one S = 1/2 spin of the Pc˙3- 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 SnIVCl2(Pc2-) to form the [(Cp*2Cr+){SnVICl2(Pc˙3-)}˙- complex but further reaction between the ions is observed. This reaction is accompanied by the substitution of one Cp* ligand of Cp*2Cr by chloride anions originating from {SnIVCl2(Pc˙3-)}˙- to form the complex {(Cp*CrCl2)(SnIV(μ-Cl)(Pc2-))}·C6H4Cl2 (2) in which the (Cp*CrCl2) and {SnIV(Pc2-)} species are bonded through the μ-bridged Cl- anion. According to the DFT calculations, this reaction proceeds via an intermediate [(Cp*2CrCl)(SnClPc)] complex.

DOI 10.1039/c7dt03807k
ISSN 1477-9234
Citation Dalton Trans. 2018;47(4):12431250.

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