Coordination of a [Co(hfac)2] moiety (hfac = hexafluoroacetylacetonate) with a nitronylnitroxide radical linked to bulky, rigid pyrene (PyrNN) gives a helical 1:1 chain complex, in which both oxygen atoms of the radical NO(·) groups are bonded to Co(II) ions with strong antiferromagnetic exchange. The complex shows single-chain magnet (SCM) behavior with frequency-dependent magnetic susceptibility, field-cooled and zero-field-cooled susceptibility divergence with a high blocking temperature of around 14 K (a record among SCMs), and hysteresis with a very large coercivity of 32 kOe at 8 K. The magnetic behavior is partly related to good chain isolation induced by the large pyrene units. Two magnetic relaxation processes have been observed, a slower one attributable to longer, and a faster one attributable to short chains. No evidence of magnetic ordering has been found.

The mixed-ligand complexes [Co(III)(tpy)(Cat-N-SQ)]Y and [Ni(II)(tpy)(Cat-N-BQ)]PF(6) (tpy = 2,2':6',2' '-terpyridine; Cat-N-BQ, Cat-N-SQ = mononegative and radical dinegative Schiff base diquinone ligand; Y = PF(6), BPh(4)) were prepared. Structural and spectroscopic data support the different charge distribution of the two compounds. The temperature-dependent electronic and spectral properties of solutions containing the [Co(III)(tpy)(Cat-N-SQ)](+) suggest that this compound undergoes a thermally driven valence tautomeric interconversion to [Co(II)(tpy)(Cat-N-BQ)](+) complex, the metal ion being in high-spin configuration. The comparison of the electrochemical properties of the cobalt and nickel derivatives supports the observed behavior. The same interconversion process was found to occur also in the solid state with a significant higher T(c) value than in solution. It was found that the previously reported [Co(III)(Cat-N-BQ)(Cat-N-SQ)] shows a similar behavior. The large difference between the interconversion T(c) in the solid state and in solution is suggested to come from the entropy changes associated with the modifications of vibronic interactions.

A structural and magnetic characterization of a trinuclear chiral Mn(II) formate three-dimensional framework exhibiting a triangular arrangement is presented. Compound Na(3)[Mn(3)(HCOO)(9)] was obtained by solvothermal synthesis and crystallizes in the chiral cubic space group P2(1)3 and is well described by a Delta conformation. The structure displays triangular Mn(3) building blocks, in which the metal centers are bonded by formate ligands in a syn-anti mode (Mn-Mn 5.697(1) A). The coordination sphere of manganese(II) is completed by six oxygen atoms from six formate ligands, resulting in an octahedral geometry. Magnetic susceptibility measurements showed antiferromagnetic interactions at high temperature and a strongly field dependent magnetic behavior below 40 K. At fields higher than 1.0 kOe only the antiferromagnetic interactions can be observed. At applied fields lower than 1.0 kOe magnetic susceptibility becomes irreversible with maxima observed at 22 and 34 K. These maxima suggest a weak ferromagnetic behavior because of spin canting, allowed by the presence of the noncentrosymmetric syn-anti HCOO bridges linking the Mn sites. This non-collinear antiferromagnetism and irreversible behavior can be due to the existence of a high degree of frustration in this unique lattice composed of linked triangular arrangements of interacting magnetic centers.

End-off bicompartmental ligands bearing a nitronyl-nitroxide arm have been designed for synthesizing various heterospin molecular systems. These ligands can selectively interact with 3d and 4f metal ions, leading to 2p-4f, 2p-3d, and 2p-3d-4f complexes. The magnetic properties of the 2p-4f and 2p-3d-4f complexes have been investigated and rationalized by theoretical calculations.

In this work we report the synthesis, crystal structures, and magnetic behavior of 2p-3d-4f heterospin systems containing the nitroxide radical 4-azido-2,2,6,6-tetramethylpiperidine-1-oxyl radical (N3tempo). These compounds were synthesized through a one-pot reaction by using [Cu(hfac)2], [Ln(hfac)3] (hfac = hexafluoroacetylacetonate, Ln = Dy(III), Tb(III) or Gd(III)), and the N3tempo radical. Depending on the stoichiometric ratio used, the synthesis leads to penta- or trimetallic compounds, with molecular formulas [Cu3Ln2(hfac)8(OH)4(N3tempo)] (Ln = Gd, Tb, Dy) and [CuLn2(hfac)8(N3tempo)2(H2O)2] (Ln = Gd, Dy). The magnetic properties of all compounds were investigated by direct current (dc) and alternating current (ac) measurements. The ac magnetic susceptibility measurements of Tb(III)- and Dy(III)-containing compounds of both families revealed slow relaxation of the magnetization, with magnetic quantum tunneling in zero field.

Two isostructural 1D complexes, [M(hfac)2NaphNN]n [M = Mn(II) (1) or Co(II) (2); NaphNN = 1-naphthyl nitronylnitroxide], were synthesized and exhibit very strong antiferromagnetic metal-radical exchange coupling. Compound 2 shows slow magnetic relaxation behavior with a high blocking temperature (TB ≈ 13.2 K) and a very high coercive field of 49 kOe at 4.0 K.

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