Self-assembly of the 4-nuclear fragment {Cu4(hfac)2(LHF)x(LF)2-x} with deprotonated trihydroxyoxanes and heterospin complexes with nitroxides

• Published in: Polyhedron 2023-01, Vol.229, p.116209, Article 116209
• Main Authors: Kuznetsova, Olga, Sayfullina, Dinara, Romanenko, Galina, Letyagin, Gleb, Bogomyakov, Artem
• Format: Article
• Language: English
• Subjects: 2,4,6-tris(trifluoromethyl)tetrahydropyran, 2,4,6-triol; 2-methyl-4, 6-bis(trifluoromethyl)tetrahydropyran, 2,4,6-triol; Copper; Crystal structure; Heterospin complexes; Hexafluoroacetylacetonate; Magnetic properties; Nitronyl nitroxide radicals
• ISSN: 0277-5387
• DOI: 10.1016/j.poly.2022.116209

Recrystallization of [Cu4(hfac)4(MeO)4] and [Cu11(hfac)10(OH)8(O)2]·2C7H8 and their interaction with nitroxides in acetone containing media led to self-assembling of complexes containing fragment {Cu4(hfac)2(LHF)x(LF)2-x} (x = 0–2), with triply-charged tetrahydropyrantriol-anions. The LHF/LF ratio is determined by the presence of base and acetone in the reaction mixture and the duration of crystallization. [Display omitted] It was shown experimentally that interaction of polynuclear hexafluoroacetylacetonates [Cu4(hfac)4(MeO)4] and [Cu11(hfac)10(OH)8(O)2]·2C7H8 with nitronyl nitroxide radicals as well as their recrystallization in the presence of acetone led to complexes containing tetranuclear fragment {Cu4(hfac)2(LHF)x(LF)2-x} (x = 0–2), where LHF and LF are triply charged anions of 2-methyl-4,6-bis(trifluoromethyl)tetrahydropyran-2,4,6-triol and 2,4,6-tris(trifluoromethyl)tetrahydropyran-2,4,6-triol, respectively. The main factors contributing to the formation of the 4-nuclear fragment and trioxanes LHF and LF were identified. It is established that self-assembly of {Cu4(hfac)2(LHF)x(LF)2-x} is observed only in the case of mono- and polynuclear CuII hexafluoroacetylacetonates. For CoII and NiII compounds the formation of such a fragment is not registered.