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Issue 15, 2014
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Doubly TEMPO-coordinated gadolinium(III), lanthanum(III), and yttrium(III) complexes. Strong superexchange coupling across rare earth ions

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Abstract

We prepared crystalline [REIII(hfac)3(TEMPO)2] (RE = Gd, La, Y), where TEMPO and hfac stand for 2,2,6,6-tetramethylpiperidin-1-oxyl and 1,1,1,5,5,5-hexafluoropentane-2,4-dionate, respectively. The X-ray crystal structure of TEMPO-coordinated RE compounds was determined for the first time. The Gd and Y analogues are isomorphous, and the La derivative has a similar molecular skeleton. The Gd–O(TEMPO) bond lengths were 2.322(3) and 2.354(3) Å with the O–Gd–O angle of 140.36(11)°. The magnetic study clarified that [Gd(hfac)3(TEMPO)2] behaved as a ground Stotal = 7/2 species. The La and Y analogues showed the superexchange interactions across the diamagnetic ions with 2JTEMPO1–TEMPO2/kB = –14.9(1) and −49.8(2) K, respectively. Assuming the presence of a similar interaction like the Y derivative, the Gd–TEMPO exchange couplings are estimated with 2JGd–TEMPO/kB = −12.9(5) and +8.0(6) K.

Graphical abstract: Doubly TEMPO-coordinated gadolinium(iii), lanthanum(iii), and yttrium(iii) complexes. Strong superexchange coupling across rare earth ions

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Publication details

The article was received on 20 Dec 2013, accepted on 30 Jan 2014 and first published on 30 Jan 2014


Article type: Paper
DOI: 10.1039/C3DT53586J
Author version available: Download Author version (PDF)
Citation: Dalton Trans., 2014,43, 5893-5898
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    Doubly TEMPO-coordinated gadolinium(III), lanthanum(III), and yttrium(III) complexes. Strong superexchange coupling across rare earth ions

    R. Murakami, T. Nakamura and T. Ishida, Dalton Trans., 2014, 43, 5893
    DOI: 10.1039/C3DT53586J

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