A supramolecular aggregate of four exchange-biased single-molecule magnets

The reaction between 3-phenyl-1,5-bis(pyridin-2-yl)pentane-1,5-dione dioxime (pdpdH(2)) and triangular Mn(III)(3)O(O(2)CMe)(py)(3)](ClO(4)) (1) affords Mn(12)O(4)(O(2)CMe)(12)(pdpd)(6))](ClO(4))(4) (3). Complex 3 has a rectangular shape and consists of four Mn(III)(3)O](7+) triangular units linked covalently by the dioximate ligands into a supramolecular Mn(3)](4) tetramer. Solid-state dc and ac magnetic susceptibility measurements revealed that Mn(3)](4) contains four Mn(3) single-molecule magnets (SMMs), each with an S = 6 ground state. Magnetization versus dc-field sweeps on a single crystal gave hysteresis loops below 1 K that exhibited exchange-biased quantum tunneling of magnetization steps, confirming 3 to be a supramolecular aggregate of four weakly exchange-coupled SMM units.