RESUMO
This article overviews the current state and prospects of the concept of advanced single-molecule magnets (SMMs) based on low-spin (S = 1/2) pentagonal-bipyramidal (PBP) 4d3 and 5d3 complexes with unquenched orbital angular momentum. This approach is based on the unique property of PBP 4d3 and 5d3 complexes to cause highly anisotropic spin coupling of perfect uniaxial symmetry, -JzSziSzj - Jxy(SxiSxj + SyiSyj), regardless of the local geometric symmetry. The M(4d/5d)-M(3d) exchange-coupled pairs in the apical positions of the PBP complexes produce Ising-type exchange interactions (|Jz| > |Jxy|), which serve as a powerful source of uniaxial magnetic anisotropy of a SMM cluster. In polynuclear heterometallic 4d/5d-3d complexes embodying PBP 4d/5d units and high-spin 3d ions, anisotropic Ising-type exchange interactions produce a double-well potential with high energy barriers Ueff, which is controlled by the anisotropic exchange parameters Jz, Jxy. Theoretical analysis shows that the barrier is proportional to the difference |Jz - Jxy| and to the number n of the apical 4d/5d-3d pairs in a SMM cluster, Ueff â |Jz - Jxy|n, which provides an opportunity to scale up the barrier Ueff and blocking temperature TB up to the record values. A novel family of 4d/5d complexes with forced PBP coordination provided by structurally rigid planar pentadentate Schiff-base ligands in the equatorial plane is discussed as a better alternative to the cyanometallates. The possibility of a significant increase in the anisotropic exchange parameters Jz, Jxy in PBP complexes with monoatomic apical µ-bridging ligands is examined. The basic principles of molecular engineering the highest barrier through anisotropic exchange interactions of PBP 4d/5d complexes are formulated. The theoretical and experimental results taken together indicate that the concept of high-performance SMMs based on 4d/5d PBP complexes with unquenched orbital angular momentum is an attractive alternative to the currently dominant lanthanide-based SMM strategy.
RESUMO
The first pentagonal-bipyramidal tungsten(III) complex (Et4N)[WIII(DAPBH)(CN)2] with a N3O2-type Schiff-base ligand and two apical cyanide groups was synthesized and characterized structurally and magnetically. The complex has a low-spin (S = 1/2) ground state and features unquenched orbital angular momentum ML = ±1 causing very strong Ising-type magnetic anisotropy.
RESUMO
The first paramagnetic pentagonal-bipyramidal complex of Mo(iii) with a N3O2-type Schiff-base ligand was synthesized by the comproportionation reaction between Mo(ii) and Mo(iv) congeners. The complex has a low-spin (S = 1/2) ground state of MoIII(4d3) with double orbital degeneracy and unquenched orbital momentum, which result in strong Ising-type magnetic anisotropy.
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A heptacoordinate complex [MoIV(DAPBH)Cl2] (H2DAPBH is 1,1'-(pyridine-2,6-diyl)bis(ethan-1-yl-1-ylidene)dibenzohydrazine) has been synthesized and characterized structurally and magnetically. It exhibits a slightly distorted pentagonal bipyramidal geometry and reveals paramagnetic behaviour resulting from two unpaired electrons (S = 1) with large positive zero-field splitting (D = +50 cm-1) and pronounced temperature-independent paramagnetism.
RESUMO
A new high symmetry Mn(12) oxocarboxylate cluster [Mn(12)O(12)(CN-o-C(6)H(4)CO(2))(12)(CH(3)CO(2))(4)(H(2)O)(4)]·8CH(2)Cl(2) (1) with mixed carboxylate ligands is reported. It was synthesized by the standard carboxylate substitution method. 1 crystallizes in the tetragonal space group I4(1)/a. Complex 1 contains a [Mn(12)O(12)] core with eight CN-o-C(6)H(4)CO(2) ligands in the axial positions, four CH(3)CO(2) and four CN-o-C(6)H(4)CO(2) in equatorial positions. Four H(2)O molecules are bonded to four Mn atoms in an alternating up, down, up, down arrangement indicating a 1 : 1 : 1 : 1 isomer. The Mn(12) molecules in 1 are self-assembled by complementary hydrogen C-H···N bonds formed with participation of the axial o-cyanobenzoate ligands of the adjacent Mn(12) clusters. The lattice solvent molecules (CH(2)Cl(2)) are weakly interacted with Mn(12) units that results in solvent loss immediately after removal of the crystals from the mother liquor. The electronic structure and the intramolecular exchange parameters have been calculated. Mn 3d bands of 1 are rather broad, and the center of gravity of the bands shifts down from the Fermi level. The overlap between Mn 3d bands and 2p ones of the oxygen atoms from the carboxylate bridges is higher than in the parent Mn(12)-acetate cluster. These changes in the electronic structure provide a significant difference in the exchange interactions in comparison to Mn(12)-acetate. The magnetic properties have been studied on a dried (solvent-free) polycrystalline sample of 1. The dc magnetic susceptibility measurements in the 2-300 K temperature range support a high-spin ground state (S = 10). A bifurcation of temperature dependencies of magnetization taken under zero field cooled and field cooled conditions observed below 4.5 K is due to slow magnetization relaxation. Magnetization versus applied dc field exhibited a stepwise hysteresis loop at 2 K. The ac magnetic susceptibility data revealed the frequency dependent out-of-phase (χ(M)'') signals characteristic of single-molecule magnets.
RESUMO
It is shown by electron paramagnetic resonance (EPR) and superconducting quantum interference device (SQUID) magnetometry that two spin systems coexist in conducting layers of the quasi-2D organic metal (BEDO-TTF)(2)ReO(4)·H(2)O: delocalized moments of charge carriers (holes), I(epr)(300 K) = 1.62 × 10(-4) emu mol(-1), and localized moments on BEDO-TTF(+1), χ(p)(300 K) = 4.25 × 10(-4) emu mol(-1). The phase transition Me-Me' at T(c) = 203 K is detected in paramagnetic relaxation, EPR amplitude and resistivity. Magnetic susceptibilities, I(epr) and χ(p), are not sensitive to the transition. Due to fine rearrangement of ReO(4) linked by H(2)O, the electronic spectrum becomes inhomogeneous. Below the transition exchange-coupled localized states within the metallic phase are observed. On cooling, the concentration of delocalized moments gradually decreases, contributing to a localized spin system. The phenomenon is interpreted in terms of short-range antiferromagnetic (AFM) interactions via conducting electrons. Below 14 K the AFM coupled states decay, and paramagnetism of local moments is recovered.
