Trinuclear linear 3d-4f-3d complexes (3d = Mn(II), Fe(II), Co(II), Zn(II) and 4f = La(III), Gd(III), Tb(III), Dy(III)) were prepared by using a tripodal nonadentate Schiff base ligand, N,N',N''-tris(2-hydroxy-3-methoxybenzilidene)-2-(aminomethyl)-2-methyl-1,3-propanediamine. The structural determinations showed that in these complexes two distorted trigonal prismatic transition metal complexes of identical chirality are assembled through 4f cations. The Mn and Fe entities crystallize in the chiral space group P2(1)2(1)2(1) as pure enantiomers; the cobalt complexes exhibit a less straightforward behavior. All Mn, Fe, and Co complexes experience M(II)-Ln(III) ferromagnetic interactions. The Mn-Gd interaction is weak (0.08 cm(-1)) in comparison to the Fe-Gd (0.69 cm(-1)) and Co-Gd (0.52 cm(-1)) ones while the single ion zero field splitting (ZFS) term D is larger for the Fe complexes (5.7 cm(-1)) than for the cobalt ones. The cobalt complexes behave as single-molecules magnets (SMMs) with large magnetization hysteresis loops, as a consequence of the particularly slow magnetic relaxation characterizing these trinuclear molecules. Such large hysteresis loops, which are observed for the first time in Co-Ln complexes, confirm that quantum tunnelling of the magnetization does not operate in the Co-Gd-Co complex.

Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {Fe(II)Nb(IV)} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb(IV), Mo(IV), W(IV)). X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H(2)O)Fe(L(1))}{M(CN)(8)}{Fe(L(1))}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L(1))}(2+) and {M(CN)(8)}(4-) units (L(1) stands for the pentadentate macrocycle). Analysis of the magnetic susceptibility behavior revealed cyano-bridged {Fe-Nb} exchange interaction to be antiferromagnetic with J = -20 cm(-1) deduced from fitting an Ising model taking into account the noncollinear spin arrangement. For this ferrimagnetic chain a slow relaxation of its magnetization is observed at low temperature revealing a SCM behavior with Delta/k(B) = 74 K and tau(0) = 4.6 x 10(-11) s. The M versus H behavior exhibits a hysteresis loop with a coercive field of 4 kOe at 1 K and reveals at 380 mK magnetic avalanche processes, i.e., abrupt reversals in magnetization as H is varied. The origin of these characteristics is attributed to the combination of efficient {Fe-Nb} exchange interaction and significant anisotropy of the {Fe(L(1))} unit. High field EPR and magnetization experiments have revealed for the parent compound [Fe(L(1))(H(2)O)(2)]Cl(2) a negative zero field splitting parameter of D approximately = -17 cm(-1). The crystal structure, magnetic behavior, and Mossbauer data for [Fe(L(1))(H(2)O)(2)]Cl(2) are also reported.