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

Journal Article · · Journal of Solid State Chemistry
 [1];  [1]; ;  [2];  [1]
  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, Vol. 183, Issue 4; Other Information: DOI: 10.1016/j.jssc.2010.02.012; PII: S0022-4596(10)00066-6; Copyright (c) 2010 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
Country of Publication:
United States
Language:
English