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Functionalized Nitronyl Nitroxide Biradicals for the Construction of 3d-4f Heterometallic Compounds

Functionalized Nitronyl Nitroxide Biradicals for the Construction of 3d-4f Heterometallic Compounds

Hongdao Li, Juan Sun, Meng Yang, Zan Sun, Jinkui Tang, Yue Ma, Licun Li

Inorg Chem. 2018 Aug 20;57(16):9757-9765.

PMID: 29420034

Abstract:

Functionalized nitronyl nitroxide biradical ligands incorporating pyridine groups hold CoII and LnIII ions together, creating biradical-based 3d-4f tetranuclear complexes [Ln2Co2(hfac)10(NITPhPybis)2] [LnIII = 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 CoII and two LnIII ions, resulting in a rare octaspin system. Direct-current (dc) magnetic susceptibility studies reveal that the strong antiferromagnetic CoII-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.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP848243254	2-Isopropoxy-3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-pyridine		848243-25-4	Price

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