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

Dmitri V Konarev; Sergey I Troyanov; Alexander F Shestakov; Evgeniya I Yudanova; Akihiro Otsuka; Hideki Yamochi; Hiroshi Kitagawa; Rimma N Lyubovskaya

doi:10.1039/c7dt03807k

Reaction of tin(iv) phthalocyanine dichloride with decamethylmetallocenes (M = Cr^II and Co^II). Strong magnetic coupling of spins in (Cp*₂Co⁺){Sn^IVCl₂(Pc˙^3-)}˙^-·2C₆H₄Cl₂

Dalton Trans. 2018 Jan 23;47(4):1243-1250. doi: 10.1039/c7dt03807k.

Authors

Dmitri V Konarev¹, Sergey I Troyanov, Alexander F Shestakov, Evgeniya I Yudanova, Akihiro Otsuka, Hideki Yamochi, Hiroshi Kitagawa, Rimma N Lyubovskaya

Affiliation

¹ Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow Region, 142432 Russia. konarev3@yandex.ru.

PMID: 29299581
DOI: 10.1039/c7dt03807k

Abstract

The reaction of tin(iv) phthalocyanine dichloride {Sn^IVCl₂(Pc^2-)} with decamethylmetallocenes (Cp*₂M, M = Co, Cr) has been studied. Decamethylcobaltocene reduces Sn^IVCl₂(Pc^2-) to form the (Cp*₂Co⁺){Sn^IVCl₂(Pc˙^3-)}˙^-·2C₆H₄Cl₂ (1) complex. The negative charge of {Sn^IVCl₂(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 1.68μ_B 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 Sn^IVCl₂(Pc^2-) to form the [(Cp*₂Cr⁺){Sn^VICl₂(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 {Sn^IVCl₂(Pc˙^3-)}˙^- to form the complex {(Cp*CrCl₂)(Sn^IV(μ-Cl)(Pc^2-))}·C₆H₄Cl₂ (2) in which the (Cp*CrCl₂) and {Sn^IV(Pc^2-)} species are bonded through the μ-bridged Cl^- anion. According to the DFT calculations, this reaction proceeds via an intermediate [(Cp*₂CrCl)(SnClPc)] complex.