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A family of five [MIII2MII3] n + trigonal bipyramidal cages (M III = Fe, Cr and Al; M II = Co, Zn and Pd; n = 0 for 1-3 and n = 6 for 4-5 ) of formulae [Fe 2 Co 3 L 6 Cl 6 ] ( 1 ), [Fe 2 Zn 3 L 6 Br 6 ] ( 2 ), [Cr 2 Zn 3 L 6 Br 6 ] ( 3 ), [Cr 2 Pd 3 L 6 (dppp) 3 ](OTf) 6 ( 4 ) and [Al 2 Pd 3 L 6 (dppp) 3 ](OTf) 6 ( 5 ) (where HL is 1-(4-pyridyl)butane-1,3-dione and dppp is 1,3-bis(diphenylphosphino)propane) are reported. Neutral cages 1-3 were synthesised using the tritopic [M III L 3 ] metalloligand in combination with the salts Co II Cl 2 and Zn II Br 2 , which both act as tetrahedral linkers. The assembly of the cis -protected [Pd II (dppp)(OTf) 2 ] with [M III L 3 ] afforded the anionic cages 4-5 of general formula [MIII2PdII3](OTf) 6 . The metallic skeleton of all cages describes a trigonal bipyramid with the M III ions occupying the two axial sites and the M II ions sitting in the three equatorial positions. Direct current (DC) magnetic susceptibility, magnetisation and heat capacity measurements on 1 reveal weak antiferromagnetic exchange between the Fe III and Co II ions. EPR spectroscopy demonstrates that the distortion imposed on the {MO 6 } coordination sphere of [M III L 3 ] by complexation in the {MIII2MII3} supramolecules results in a small, but measurable, increase of the zero field splitting at M III . Complete active space self-consistent field (CASSCF) calculations on the three unique Co II sites of 1 suggest D Co ≈ -14 cm -1 and E / D ≈ 0.1, consistent with the magnetothermal and spectroscopic data.

We characterize supramolecular magnetic structures, consisting of two weakly coupled antiferromagnetic rings, by low-temperature specific heat, susceptibility, magnetization and electron paramagnetic resonance measurements. Intra- and inter-ring interactions are modeled through a microscopic spin-Hamiltonian approach that reproduces all the experimental data quantitatively and legitimates the use of an effective two-qubit picture. Spin entanglement between the rings is experimentally demonstrated through magnetic susceptibility below 50 mK and theoretically quantified by the concurrence.

Crystals containing Ni10 magnetic molecules display an unprecedented form of out-of-equilibrium behavior of the bulk magnetization M at temperatures as high as 17 K. We have performed 1H NMR measurements to probe the local Ni magnetic moments and their dynamics. It is apparent that no freezing of the Ni moments occurs, in striking contrast to what is observed in blocked superparamagnetic systems. The average local moments display the same behavior as M, thus unambiguously demonstrating the intrinsic character of the phenomenon. This result supports the hypothesis that the slowing down of M is due to a resonant phonon trapping mechanism which prevents the thermalization of M but not the fast spin flippings of the individual molecular moments. Indeed, the measured nuclear spin-lattice relaxation rate points to fast single-molecule dynamics at low temperature.

We investigate a family of molecular crystals containing noninteracting Ni10 magnetic molecules. We find slow relaxation of the magnetization below a temperature as high as 17 K and we show that this behavior is not associated with an anisotropy energy barrier. Ni10 has a characteristic magnetic energy spectrum structured in dense bands, the lowest of which makes the crystal opaque to phonons of energy below about 1 meV. We ascribe the nonequilibrium behavior to the resulting resonant trapping of these low-energy phonons. Trapping breaks up spin relaxation paths leading to a novel kind of slow magnetic dynamics which occurs in the lack of anisotropy, magnetic interactions and quenched disorder.