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Issue 18, 2010
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A homologous heterospin series of mononuclear lanthanide/TCNQF4 organic radical complexes

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Abstract

Reactions between trivalent rare earth ions (MIII = La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er and Yb) and the radical anion of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (TCNQF4) produce a family of mononuclear complexes {M[(TCNQF4)]2[H2O]x}·(TCNQF4)(3H2O), x = 6, 7. The cationic complex {MIII([TCNQF4]˙)2[H2O]x}+ cocrystallizes with one [TCNQF4]˙ radical anion and three water molecules. One of the coordinated [TCNQF4]˙ radicals is involved in π–π stacking interactions with the uncoordinated [TCNQF4]˙ radicals which leads to the antiferromagnetic coupling for these ((TCNQF4)2)2−π-dimers. The second coordinated [TCNQF4]˙ remains as a radical ligand and is not involved in π–π interactions. Magnetic studies indicate that the Sm compound magnetically orders at 4.4 K and that a fraction of the Gd and Dy samples undergo magnetic ordering at 3.7 K and 4.3 K respectively due to partial dehydration (loss of interstitial water molecules). Diamagnetic metal ions were used to generate magnetically dilute Gd, and Dy compounds that do not exhibit any signs of magnetic ordering.

Graphical abstract: A homologous heterospin series of mononuclear lanthanide/TCNQF4 organic radical complexes

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Publication details

The article was received on 23 Oct 2009, accepted on 10 Feb 2010 and first published on 29 Mar 2010


Article type: Paper
DOI: 10.1039/B922219G
Citation: Dalton Trans., 2010,39, 4341-4352
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    A homologous heterospin series of mononuclear lanthanide/TCNQF4 organic radical complexes

    N. Lopez, H. Zhao, A. V. Prosvirin, W. Wernsdorfer and K. R. Dunbar, Dalton Trans., 2010, 39, 4341
    DOI: 10.1039/B922219G

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