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Strongest Ferromagnetic Coupling in Designed Gadolinium(III)–Nitroxide Coordination Compounds
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- Takuya Kanetomo
- Department of Engineering Science, The University of Electro-Communications, Chofu, Tokyo 182-8585, Japan
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- Toru Yoshitake
- Department of Engineering Science, The University of Electro-Communications, Chofu, Tokyo 182-8585, Japan
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- Takayuki Ishida
- Department of Engineering Science, The University of Electro-Communications, Chofu, Tokyo 182-8585, Japan
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Description
Three novel gadolinium(III)-radical complexes [Gd(III)(hfac)3(H2O)(L)] [Gd-L; L = tert-butyl phenyl nitroxide (phNO) and its derivatives (tert-butyl 3-tolyl nitroxide and tert-butyl 4-tert-butylphenyl nitroxide)] were synthesized, and all compounds showed ferromagnetic coupling, obeying the empirical relation: out-of-plane coordination of the Gd ion from the radical π system favors ferromagnetic coupling. In particular, Gd-phNO has a considerably large torsion angle around Gd-O-N-Csp(2) (69.8(9)° on average) and the largest ferromagnetic coupling parameter (2J/kB = +18.0(4) K) in Gd-nitroxide compounds ever known. The validity of our molecular design was assessed on the basis of the magneto-structure relation analysis with many literature data including various paramagnetic ligating groups.
Journal
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- Inorganic Chemistry
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Inorganic Chemistry 55 (16), 8140-8146, 2016-08-02
American Chemical Society (ACS)
