Calix[4]arene clusters as enhanced magnetic coolers and molecular magnets

Georgios Karotsis, Stuart Kennedy, Simon J. Teat, Christine M. Beavers, Drew A. Fowler, Juan J. Morales, Marco Evangelisti, Scott J. Dalgarno, Euan K. Brechin

Research output: Contribution to journalArticlepeer-review

266 Citations (Scopus)


The use of methylene-bridged calix[4]arenes in 3d/4f chemistry produces a family of clusters of general formula [MnIII4Ln III4(OH)4(C4)4(NO3) 2(DMF)6(H2O)6](OH)2 (where C4 = calix[4]arene; Ln = Gd (1), Tb (2), Dy (3)). The molecular structure describes a square of LnIII ions housed within a square of Mn III ions. Magnetic studies reveal that 1 has a large number of molecular spin states that are populated even at the lowest investigated temperatures, while the ferromagnetic limit S = 22 is being approached only at the highest applied fields. This, combined with the high magnetic isotropy, makes the complex an excellent magnetic refrigerant for low-temperature applications. Replacement of the isotropic GdIII ions with the anisotropic TbIII and DyIII ions "switches" the magnetic properties of the cluster so that 2 and 3 behave as low-temperature molecular magnets, displaying slow relaxation of the magnetization. © 2010 American Chemical Society.

Original languageEnglish
Pages (from-to)12983-12990
Number of pages8
JournalJournal of the American Chemical Society
Issue number37
Publication statusPublished - 22 Sept 2010


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