Journal of the American Chemical Society 2008-08-20

Mixed-valent Mn supertetrahedra and planar discs as enhanced magnetic coolers.

Maria Manoli, Anna Collins, Simon Parsons, Andrea Candini, Marco Evangelisti, Euan K Brechin

Index: J. Am. Chem. Soc. 130 , 11129-39, (2008)

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Abstract

The syntheses and structures of two decametallic mixed-valent Mn supertetrahedra using 2-amino-2-methyl-1,3-propanediol (ampH2), two decametallic mixed-valent Mn planar discs using 2-amino-2-methyl-1,3-propanediol (ampH2) and 2-amino-2-ethyl-1,3-propanediol (aepH2), and a tetradecametallic mixed-valent Mn planar disc using pentaerythritol (H4peol) are reported. The decametallic complexes display dominant ferromagnetic exchange and spin ground states of S = 22, and the tetradecametallic complex displays dominant antiferromagnetic exchange and a spin ground state of S = 7 +/- 1. All display large (the former) and enormous (the latter) magnetocaloric effect--the former as a result of negligible zero-field splitting of the ground state, and the latter as a result of possessing a high spin-degeneracy at finite low temperatures--making them the very best cooling refrigerants for low-temperature applications.