Two tri-spin complexes based on gadolinium and nitronyl nitroxide radicals: Structure and ferromagnetic interactions

Journal Article · Thu Apr 15 04:00:00 EDT 2010 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2010.02.012· OSTI ID:21372574

Na, Zhou ^[1]; Chao, Wang ^[1]; Gongfeng, Xu; Jinkui, Tang ^[2]; Shiping, Yan ^[1]

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1. Department of Chemistry, Nankai University, Tianjin 300071 (China)
2. State Key Laboratory of Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Science, Changchun 130022 (China)

Three Radical-Ln(III)-Radical complexes based on nitronyl nitroxide radicals have been synthesized, structurally and magnetically characterized: [Gd(hfac){sub 3}(NITPhOEt){sub 2}] (1) (hfac=hexafluoroacetylacetonate, and NITPhOEt=4'-ethoxy-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), [Gd(hfac){sub 3}(NITPhOCH{sub 2}Ph){sub 2}] (2) (NITPhOCH{sub 2}Ph=4'-benzyloxy-phenyl-4,4,5, 5-tetramethylimidazoline-1-oxyl-3-oxide) and [Lu(hfac){sub 3}(NITPhOCH{sub 2}Ph){sub 2}] (3). The X-ray crystal structure analyses show that the structures of the three compounds are similar and all consist of the isolated molecules, in which central ions Gd{sup III} or Lu{sup III} are coordinated by six oxygen atoms from three hfac and two oxygen atoms from nitronyl radicals. The magnetic studies show that in both of the two Gd{sup III} complexes, there are ferromagnetic Gd{sup III}-Rad interactions and antiferro-magnetic Rad-Rad interactions in the molecules (with J{sub Rad-Gd}=0.27 cm{sup -1}, j{sub Rad-Rad}=-2.97 cm{sup -1} for 1: and J{sub Rad-Gd}=0.62 cm{sup -1}, j{sub Rad-Rad}=-7.01 cm{sup -1} for 2). An analogous complex of [Lu(hfac){sub 3} (NITPhOCH{sub 2}Ph){sub 2}] (3) containing diamagnetic Lu{sup III} ions has also been introduced for further demonstrating the nature of magnetic coupling between radicals. - Graphical abstract: Two tri-spin complexes based on gadolinium-radical have been synthesized and characterized, the magnetic studies show that in the two complexes the Gd-radical interaction is ferromagnetic and the radical-radical interaction is antiferromagnetic. An analogous complex containing the diamagnetic Lu{sup III} ions has also been synthesized to further demonstrate the nature of the magnetic coupling between radicals.

• OSTI ID: 21372574
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 4 Vol. 183; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ANTIFERROMAGNETISM
CHALCOGENIDES
CHARGED PARTICLES
COMPLEXES
CRYSTAL STRUCTURE
GADOLINIUM COMPLEXES
GADOLINIUM IONS
INTERACTIONS
IONS
LUTETIUM COMPLEXES
LUTETIUM IONS
MAGNETISM
OXIDES
OXYGEN COMPOUNDS
RADICALS
RARE EARTH COMPLEXES