Heterotrimetallic paramagnetic complex of ring reduced tin() hexadecachlorophthalocyanine

Coordination complex (Cp* 2 Cr III ) + {CpFe II (CO) 2 (Sn II [PcCl 16 ] 4− )} − ( 1 ) has been obtained by the reduction of tin( iv ) dichloride hexadecachlorophthalocyanine (PcCl 16 ) by decamethylchromocene (Cp* 2 Cr) in the presence of {CpFe I (CO) 2 } 2 . The process is accompanied by oxidation...

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Published in:New journal of chemistry 2023-04, Vol.47 (14), p.6924-6931
Main Authors: Romanenko, Nikita R, Faraonov, Maxim A, Osipov, Nikita G, Kuzmin, Alexey V, Khasanov, Salavat S, Otsuka, Akihiro, Yamochi, Hideki, Kitagawa, Hiroshi, Konarev, Dmitri V
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Language:English
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Summary:Coordination complex (Cp* 2 Cr III ) + {CpFe II (CO) 2 (Sn II [PcCl 16 ] 4− )} − ( 1 ) has been obtained by the reduction of tin( iv ) dichloride hexadecachlorophthalocyanine (PcCl 16 ) by decamethylchromocene (Cp* 2 Cr) in the presence of {CpFe I (CO) 2 } 2 . The process is accompanied by oxidation of Cr II and Fe I centers and the formation of paramagnetic Cr III and diamagnetic Fe II species. Two-electron reduction of a macrocycle and the formation of diamagnetic [PcCl 16 ] 4− as well as a transition of tin( iv ) to tin( ii ) occur. The [PcCl 16 ] 4− tetraanions are formed in (cryptand(K + )) 2 {Sn IV Cl 2 [PcCl 16 ] 4− } 2− ·2C 6 H 4 Cl 2 ( 2 ) obtained by the reduction of Sn IV PcCl 16 by mild reductant - fullerene C 60 &z.rad; − radical anions. Complexes 1 and 2 precipitate as crystals. Sandwich-type assemblies are formed in 1 . Two (Cp* 2 Cr III ) + cations are sandwiched between two {CpFe II (CO) 2 (Sn II [PcCl 16 ] 4− )} − planes, whereas layers of the {Sn IV Cl 2 [PcCl 16 ] 4− } 2− macrocycles are formed in 2 . The formation of the [PcCl 16 ] 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 Cr III spin ( S = 3/2) per formula unit. Weak antiferromagnetic coupling is observed between the spins. Only Cr III atoms contribute to EPR spectra of 1 , whereas salt 2 is diamagnetic and EPR silent. The crystalline paramagnetic complex based on ring-reduced tin( ii ) hexadecachlorophthalocyanine has been obtained and characterized. Two paramagnetic (Cp* 2 Cr III ) + cations are sandwiched between the diamagnetic {CpFe II (CO) 2 (Sn II [PcCl 16 ] 4− )} − anions.
ISSN:1144-0546
1369-9261
DOI:10.1039/d3nj00506b