The Properties of the [Mn12O12(O2CR)16(H2O)4] Single-Molecule Magnets in Truly Axial Symmetry: [Mn12O12(O2CCH2Br)16(H2O)4]·4CH2Cl2

Abstract

Detailed studies are reported of a Mn(12) single-molecule magnet (SMM) in truly axial (tetragonal) symmetry. The complex is [Mn(12)O(12)(O(2)CCH(2)Br)(16)(H(2)O)(4)].4CH(2)Cl(2) (2.4CH(2)Cl(2) or Mn(12)-BrAc), obtained by the standard carboxylate substitution method. The complex has an S = 10 ground state, typical of the Mn(12) family, and displays frequency-dependent out-of-phase AC susceptibility signals and hysteresis in single-crystal magnetization vs applied DC field sweeps. Single-crystal high-frequency EPR spectra in frequencies up to 360 GHz exhibit narrow signals that are not overlapping multiplets, in contrast to [Mn(12)O(12)(O(2)CMe)(16)(H(2)O)(4)].2MeCO(2)H.4H(2)O (1 or Mn(12)-Ac), which also crystallizes in an axial (tetragonal) space group but which now is recognized to consist of a mixture of six hydrogen-bonded isomers in the crystal and thus gives multiple, inhomogeneously broadened EPR signals. Similarly, single-crystal (55)Mn NMR spectra on Mn(12)-BrAc display much sharper signals than a single crystal of Mn(12)-Ac, and this allows one Mn(III) signal to show an almost baseline-resolved quintet from quadrupolar splitting ((55)Mn, I = 5/2, 100%), allowing quadrupole coupling parameters (e(2)qQ) to be determined. In addition, it was found that crushing crystals of Mn(12)-BrAc into a microcrystalline powder causes severe broadening and shifts of the NMR resonances, emphasizing the superiority of single-crystal studies. The combined results establish that Mn(12)-BrAc is far superior to Mn(12)-Ac for the study of the intrinsic properties of the Mn(12) family of SMMs in axial symmetry, and for the search for new phenomena such as quantum interference effects caused by higher-order (>2nd-order) transverse terms in the spin Hamiltonian.