Profiting from a multicoordinating nitronyl nitroxide radical, i.e. a functionalized nitronyl nitroxide biradical ligand, a family of novel tetranuclear lanthanide complexes, formulated as [RE 4 (hfac) 12 (NITPhO-3Pybis) 2 ] (RE = Gd 1, Tb 2, Dy 3, Ho 4, and Y 5; NITPhO-3Pybis = 5-(3-pyridinyloxy)-1,3-bis(1′-oxyl-3′-oxido-4′,4′,5′,5′-tetramethyl-4,5-hydro-1H-imidazol-2-yl)benzene; hfac = hexafluoroacetylacetonate) were successfully constructed and characterized. In these complexes, the designed functionalized nitronyl nitroxide biradical ligand functions as the chelating and/or bridging ligand to bind the lanthanide ions, resulting in tetranuclear octa-spin lanthanide complexes with a circle-shaped arrangement. Direct-current magnetic data show that antiferromagnetic interaction dominates in the Gd derivative, while ferromagnetic coupling plays a leading role in complex Y, in which the relevant magnetic exchange parameters were obtained through applicable magnetic models. Dynamic magnetic studies of Tb and Dy analogues exhibit apparent frequency-dependent out-ofphase signals, which are typical features for slow magnetic relaxation behavior. The values of U eff and τ 0 were obtained as follows: U eff = 10.5 K and τ 0 = 6.6 × 10 −7 s for the Tb complex and U eff = 5.2 K and τ 0 = 2.5 × 10 −6 s for the Dy compound. Intriguingly, the butterfly shaped hysteresis loop is found for the Tb analogue. Guided by fluorescence spectra, the representative peaks are identified for the Tb derivative.

Functionalized nitronyl nitroxide biradical ligands incorporating pyridine groups hold Co and Ln ions together, creating biradical-based 3d-4f tetranuclear complexes [LnCo(hfac)(NITPhPybis)] [Ln = Gd (1), Tb (2), Dy (3), and Ho (4); NITPhPybis = 5-(4-pyridyl)-1,3-bis(1'-oxyl-3'-oxido-4',4',5',5'-tetramethyl-4,5-hydro-1 H-imidazol-2-yl)benzene; hfac = hexafluoroacetylacetonate]. These complexes have a centrosymmetric cyclic molecular structure in which two biradicals perform as tetradentate ligands to bind two Co and two Ln ions, resulting in a rare octaspin system. Direct-current (dc) magnetic susceptibility studies reveal that the strong antiferromagnetic Co-NO magnetic exchange dominates the present magnetic system, while magnetic coupling of Gd-ON is ferromagnetic. Analysis of the magnetic data of the Gd complex allows us to determine the magnetic parameters through the appropriate magnetic model. Alternating-current (ac) magnetic susceptibility investigations indicate that 2 displays frequency-dependent out-of-phase signals under a zero dc field, while ac magnetic susceptibilities of 3 show field-induced frequency dependence, which is a typical feature of slow relaxation of the magnetization. Complexes 1-4 represent the first nitronyl nitroxide biradical-based 3d-4f compounds.

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The first examples of Ln-nitronyl nitroxide 1D chains based on the functionalized nitronyl nitroxide biradical have been obtained, and complexes Dy and Tb exhibit slow magnetic relaxation behavior.