Hetero-tri-spin [2p-3d-4f] chain compounds based on nitronyl nitroxide lanthanide metallo-ligands: Synthesis, structure, and magnetic properties

M. Zhu (1, 2, 3) , P. Hu (1, 2, 3) , Y. Li (1, 2, 3) , X. Wang (1, 2, 3) , L. Li (1, 2, 3) , D. Liao (1, 2, 3) , V. M. L. Durga prasad goli (4) , S. Ramasesha (4) , J.-P. Sutter (5)

1 Key Laboratory of Advanced Energy Materials Chemistry, Nankai University
2 Key Laboratory of Metal and Molecule-based Material Chemistry, Nankai University
3 Collaborative Innovation Center of Chemical Science and Engineering [Tianjin, China]
4 Solid State and Structural Chemistry Unit, Indian Institute of Science
5 LCC - Laboratoire de chimie de coordination

Employing nitronyl nitroxide lanthanide(III) complexes as metallo-ligands allowed the efficient and highly selective preparation of three series of unprecedented hetero-tri-spin (CuLn-radical) one-dimensional compounds. These 2p–3d–4f spin systems, namely [Ln3Cu(hfac)11(NitPhOAll)4] (LnIII=Gd 1Gd, Tb 1Tb, Dy 1Dy; NitPhOAll=2-(4′-allyloxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), [Ln3Cu(hfac)11(NitPhOPr)4] (LnIII=Gd 2Gd, Tb 2Tb, Dy 2Dy, Ho 2Ho, Yb 2Yb; NitPhOPr=2-(4′-propoxyphenyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) and [Ln3Cu(hfac)11(NitPhOBz)4] (LnIII=Gd 3Gd, Tb 3Tb, Dy 3Dy; NitPhOBz=2-(4′-benzyloxyphenyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) involve O-bound nitronyl nitroxide radicals as bridging ligands in chain structures with a [Cu-Nit-Ln-Nit-Ln-Nit-Ln-Nit] repeating unit. The dc magnetic studies show that ferromagnetic metal–radical interactions take place in these hetero-tri-spin chain complexes, these and the next-neighbor interactions have been quantified for the Gd derivatives. Complexes 1Tb and 2Tb exhibit frequency dependence of ac magnetic susceptibilities, indicating single-chain magnet behavior.

Domaines: Chimie de coordination

M. Zhu, P. Hu, Y. Li, X. Wang, L. Li, et al.. Hetero-tri-spin [2p-3d-4f] chain compounds based on nitronyl nitroxide lanthanide metallo-ligands: Synthesis, structure, and magnetic properties. Chemistry - A European Journal, 2014, 20 (41), pp.13356-13365. ⟨10.1002/chem.201403581⟩. ⟨hal-02023185⟩