Issue 4, 2018

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

Abstract

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.

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

Supplementary files

Article information

Article type
Paper
Submitted
10 Oct 2017
Accepted
13 Dec 2017
First published
13 Dec 2017
This article is Open Access
Creative Commons BY license

Dalton Trans., 2018,47, 1243-1250

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

D. V. Konarev, S. I. Troyanov, A. F. Shestakov, E. I. Yudanova, A. Otsuka, H. Yamochi, H. Kitagawa and R. N. Lyubovskaya, Dalton Trans., 2018, 47, 1243 DOI: 10.1039/C7DT03807K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements