Mixed-Valent Mn Supertetrahedra and Planar Discs as Enhanced Magnetic Coolers

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.