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Heterotrimetallic paramagnetic complex of ring reduced tin(ii) hexadecachlorophthalocyanine†
Nikita R. Romanenko,Maxim A. Faraonov,Nikita G. Osipov,Alexey V. Kuzmin,Salavat S. Khasanov,Akihiro Otsuka,Hideki Yamochi,Hiroshi Kitagawa,Dmitri V. Konarev
New Journal of Chemistry Pub Date : 03/16/2023 00:00:00 , DOI:10.1039/D3NJ00506B
Abstract

Coordination complex (Cp*2CrIII)+{CpFeII(CO)2(SnII[PcCl16]4−)} (1) has been obtained by the reduction of tin(IV) dichloride hexadecachlorophthalocyanine (PcCl16) by decamethylchromocene (Cp*2Cr) in the presence of {CpFeI(CO)2}2. The process is accompanied by oxidation of CrII and FeI centers and the formation of paramagnetic CrIII and diamagnetic FeII species. Two-electron reduction of a macrocycle and the formation of diamagnetic [PcCl16]4− as well as a transition of tin(IV) to tin(II) occur. The [PcCl16]4− tetraanions are formed in (cryptand(K+))2{SnIVCl2[PcCl16]4−}2−·2C6H4Cl2 (2) obtained by the reduction of SnIVPcCl16 by mild reductant – fullerene C60˙ radical anions. Complexes 1 and 2 precipitate as crystals. Sandwich-type assemblies are formed in 1. Two (Cp*2CrIII)+ cations are sandwiched between two {CpFeII(CO)2(SnII[PcCl16]4−)} planes, whereas layers of the {SnIVCl2[PcCl16]4−}2− macrocycles are formed in 2. The formation of the [PcCl16]4− tetraanions in both 1 and 2 is supported by the data of structural analysis, optical spectroscopy and magnetic measurements. Susceptibility measurements correspond to the contribution of one non-interacting CrIII spin (S = 3/2) per formula unit. Weak antiferromagnetic coupling is observed between the spins. Only CrIII atoms contribute to EPR spectra of 1, whereas salt 2 is diamagnetic and EPR silent.

Graphical abstract: Heterotrimetallic paramagnetic complex of ring reduced tin(ii) hexadecachlorophthalocyanine
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