Supramolecular heptanuclear Ln–Cu complexes involving nitronyl nitroxide biradicals: structure and magnetic behavior

Lu Xi (1) , Chao-Yi Jin (1) , Hong-Wei Song (1) , Xiao-Tong Wang (1) , Li-Cun Li (1) , J. P. Sutter (2)

1 Key Laboratory of Advanced Energy Materials Chemistry, Nankai University
2 LCC - Laboratoire de chimie de coordination

Four novel heptanuclear Ln–Cu complexes with the formula [Ln2Cu(hfac)8(NITPhTzbis)2][LnCu(hfac)5(NITPhTzbis)]2 (LnCu = YCu 1, TbCu 2, DyCu 3 and HoCu 4; hfac = hexafluoroacetylacetonate) were successfully constructed by employing the triazole functionalized nitronyl nitroxide biradical ligand NITPh-Tzbis (NITPh-Tzbis = 5-(1,2,4-triazolyl)-1,3-bis(1′-oxyl-3′-oxido-4′,4′,5′,5′-tetramethyl-4,5-hydro-1H-imidazol-2-yl)benzene). These hetero-tri-spin complexes are composed of two biradical-bridged dinuclear [(LnCu(hfac)5(NITPhTzbis)] units and one trinuclear [Ln2Cu(hfac)8(NITPhTzbis)2] unit which form a heptanuclear supramolecular structure through π–π interactions. Magnetic susceptibility investigations indicate that ferromagnetic exchange interactions dominate at low temperature for this supramolecular system which can be attributed to the Ln–nitroxide exchange and intramolecular NIT⋯NIT coupling mediated by the m-phenylene moiety. The DyCu derivative was found to exhibit a slow magnetic relaxation behavior.

Domaines: Chimie de coordination

Lu Xi, Chao-Yi Jin, Hong-Wei Song, Xiao-Tong Wang, Li-Cun Li, et al.. Supramolecular heptanuclear Ln–Cu complexes involving nitronyl nitroxide biradicals: structure and magnetic behavior. Dalton Transactions, 2022, 51 (17), pp.6955-6963. ⟨10.1039/D2DT00220E⟩. ⟨hal-03673824⟩