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Comptes Rendus Chimie
Volume 15, n° 7
pages 639-646 (juillet 2012)
Doi : 10.1016/j.crci.2012.05.015
Received : 5 February 2012 ;  accepted : 21 May 2012
A family of dodecanuclear Mn11 Ln single-molecule magnets
 

Valeriu Mereacre a, Yanhua Lan a, Wolfgang Wernsdorfer b, Christopher E. Anson a, Annie K. Powell a, c,
a Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Engesserstrasse 15, 76131 Karlsruhe, Germany 
b Institut Néel–CNRS, 38042 Grenoble cedex 9, France 
c Institute of Nanotechnology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany 

Corresponding author.
Abstract

A series of four isostructural dodecanuclear complexes [MnIII9 MnII2 LnIII(O)8 (OH)(piv)16 (NO3 )(CH3 CN)]·x CH3 CN·y C7 H16 (piv=pivalate; x =½, y =¾, Ln=Tb (1); x =2, y =½, Ln=Dy (2), Ho (3), and Y (4)) has been prepared for which the structural motif described as ‘a lanthanide ion nested in a large manganese shell’ is observed. All compounds show out-of-phase signals in their ac susceptibilities, and their single-molecule magnet behaviour was confirmed by single-crystal micro-SQUID studies of 1-3 which show hysteresis loops of molecular origin at T <1.0K. The SMM behaviour observed in compounds 1-3 is more pronounced than that for 4, which contains the diamagnetic YIII ion. This is principally the result of ferromagnetic coupling between the paramagnetic anisotropic LnIII ions (TbIII, DyIII and HoIII) and the manganese shell, which enhances the total spin ground state of the complexes.

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Keywords : Manganese, Lanthanides, Structure elucidation, Magnetic properties, Single-molecule magnets




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