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• W2037700960 abstract "A carboxy-substituted alkylammonium salt, namely, (4-carboxybenzyl)tributylammonium hexafluorophosphate, ZHPF6, was prepared and used as incoming carboxylate ligand in a ligand-exchange reaction with [Mn12O12(O2CCH3)16(H2O)4] (1) to afford a new Mn12 single-molecule magnet (SMM), [Mn12O12(Z)16(H2O)4][PF6]16 (2), bearing 16 cationic units appended in the periphery. This compound behaves as a single-molecule magnet, exhibiting an out-of-phase ac magnetic susceptibility χ‘ ‘M signal that shows a single maximum in the 3.1−5.4 K temperature range. The frequency dependence of the maximum follows an Arrhenius law, with an effective energy barrier for reorientation of the spins Ueff = 53 K. The reduced magnetization versus H/T data at different temperatures were fitted by using a Hamiltonian containing Zeeman, axial, and quartic zero-field splitting terms. The expected spin ground state S = 10 was found, and the least-squares fit afforded the following zero-field-splitting parameters: D = −0.44 cm-1; B40 = 0.12 × 10-4 cm-1. Magnetization hysteresis loops were observed for 2, with a coercive field Hc = 0.34 T. Complex 2 has been used as countercation in the preparation of a family of hybrid salts containing different polyoxometalate anions, [Mn12O12(Z)16(H2O)4][W6O19]8 (3), [Mn12O12(Z)16(H2O)4][PW12O40]16/3 (4), [Mn12O12(Z)16(H2O)4][(H3O)PW11O39Ni]4 (5), and [Mn12O12(Z)16(H2O)4][(H3O)PW11O39Co]4 (6). 3−6 exhibit typical magnetic hysteresis loops with higher coercive fields for the complexes containing diamagnetic polyanions: Hc = 0.075 T (3), 0.046 T (4), 0.016 T (5), and 0.0075 T (6). However, the dynamics of the magnetic behavior below the blocking temperature is similar in all compounds. Broad frequency-dependent out-of-phase ac susceptibility signals are observed, presumably due to mixtures of different Jahn−Teller isomers. Their temperature dependence is also typical of an activated-energy process, with effective energy barriers in the 50 K range, irrespective of the nature of the polyoxoanion (diamagnetic, as in 3 and 4, or paramagnetic, as in 5 and 6). These findings seem to discard any influence of the polyoxometalate in the magnetic properties of the SMM." @default.
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• W2037700960 date "2003-11-04" @default.
• W2037700960 modified "2023-09-23" @default.
• W2037700960 title "Cationic Mn₁₂ Single-Molecule Magnets and Their Polyoxometalate Hybrid Salts" @default.
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• W2037700960 doi "https://doi.org/10.1021/ic034407r" @default.
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