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We report the synthesis, crystal structure and magnetic properties of the new heptacoordinated mononuclear erbium(III) complex (Et3NH)[Er(H2DAPS)Cl2] (H4DAPS = 2,6-diacetylpyridine bis-(salicylhydrazone)) (1). The coordination polyhedron around the Er(III) ion features a slightly distorted pentagonal bipyramid formed by the pentagonal N3O2 chelate ring of the H2DAPS ligand in the equatorial plane and two apical chloride ligands. Detailed high-frequency/high-field electron paramagnetic resonance (HF-EPR) studies of 1 result in the precise determination of the crystal field (CF) splitting energies (0, 290 and 460 GHz) and effective g-values of the three lowest Kramers doublets (KDs) of the Er(III) ion. The obtained HF-EPR data are in good agreement with the results from CF analysis for the Er(III) ion based on the simulation of the dc magnetic data of 1. The results from dynamic susceptibility measurements indicate that there is no slow relaxation of magnetisation behaviour. This observation is discussed in terms of the electronic structure of 1 obtained from experimental and theoretical results. [ABSTRACT FROM AUTHOR]

A series of three mononuclear pentagonal-bipyramidal V(III) complexes with the equatorial pentadentate N3O2 ligand (2,6-diacethylpyridinebis(benzoylhydrazone), H2DAPBH) in the different charge states (H2DAPBH0, HDAPBH1−, DAPBH2−) and various apical ligands (Cl−, CH3OH, SCN−) were synthesized and characterized structurally and magnetically: [V(H2DAPBH)Cl2]Cl·C2H5OH (1), [V(HDAPBH)(NCS)2]·0.5CH3CN·0.5CH3OH (2) and [V(DAPBH)(CH3OH)2]Cl·CH3OH (3). All three complexes reveal paramagnetic behavior, resulting from isolated S = 1 spins with positive zero-field splitting energy expected for the high-spin ground state of the V3+ (3d2) ion in a PBP coordination. Detailed high-field EPR measurements for compound 3 show that its magnetic properties are best described by using the spin Hamiltonian with the positive ZFS energy (D = +4.1 cm−1) and pronounced dimer-like antiferromagnetic spin coupling (J = −1.1 cm−1). Theoretical analysis based on superexchange calculations reveals that the long-range spin coupling between distant V3+ ions (8.65 Å) is mediated through π-stacking contacts between the planar DAPBH2− ligands of two neighboring [V(DAPBH)(CH3OH)2]+ complexes. [ABSTRACT FROM AUTHOR]

Isostructural mononuclear complexes of heavy lanthanides with the pentadentate Schiff-base dapsc ligand were synthesized, [Ln(H2dapsc)(H2O)4](NO3)3 (Ln = Tb, Dy, Ho, Er), and characterized structurally and magnetically. AC magnetic susceptibility measurements revealed that complexes of Dy3+ and Er3+ Kramers ions are field-induced single-ion magnets whereas the Tb and Ho complexes show no slow magnetic relation in DC fields up to 6000 Oe. DC and AC magnetic properties of these complexes were rationalized in terms of superposition crystal-field model calculations for Ln3+ ions, which have resulted in good agreement between the experiment and the theory. It is shown that low single-molecule magnet characteristics of the Dy and Er complexes and the absence of slow-magnetic relaxation in the Tb and Ho complexes are primarily due to the low-symmetry coordination of Ln3+ ions. [ABSTRACT FROM AUTHOR]

The crystals of a perylene complex with the polymeric cluster containing [Mn6O2(O2CCHCl2)10(H2O)2] units assembled by 3,10-perylenequinone bridges, {[Mn6O2(O2CCHCl2)10(H2O)2(C20H10O2)]2n·(C20H12)n} (I), were obtained in the reaction of [Mn12O12(O2CCHCl2)16(H2O)4] with perylene. Unlike the Mn12 oxodichloroacetate cluster, the reaction of the Mn12 oxobenzoate cluster, [Mn12O12(O2CPh)16(H2O)4], with perylene does not occur. However, it turned out that the crystals isolated from the reaction are a new Mn12 oxobenzoate cluster containing three molecules of coordinated H2O and solvate molecules of hexane, [Mn12O12(O2CC6H5)16(H2O)3]·2C6H12 (II). Crystal structures of complexes I and II as well as the magnetic properties of the former were studied. [ABSTRACT FROM AUTHOR]

We report the synthesis, crystal structure and magnetic properties of the new heptacoordinated mononuclear erbium(III) complex (Et 3 NH)[Er(H 2 DAPS)Cl 2 ] (H 4 DAPS = 2,6-diacetylpyridine bis-(salicylhydrazone)) (1). The coordination polyhedron around the Er(III) ion features a slightly distorted pentagonal bipyramid formed by the pentagonal N 3 O 2 chelate ring of the H 2 DAPS ligand in the equatorial plane and two apical chloride ligands. Detailed high-frequency/high-field electron paramagnetic resonance (HF-EPR) studies of 1 result in the precise determination of the crystal field (CF) splitting energies (0, 290 and 460 GHz) and effective g -values of the three lowest Kramers doublets (KDs) of the Er(III) ion. The obtained HF-EPR data are in good agreement with the results from CF analysis for the Er(III) ion based on the simulation of the dc magnetic data of 1. The results from dynamic susceptibility measurements indicate that there is no slow relaxation of magnetisation behaviour. This observation is discussed in terms of the electronic structure of 1 obtained from experimental and theoretical results.

A series of three mononuclear pentagonal-bipyramidal V(iii) complexes with the equatorial pentadentate N3O2 ligand (2,6-diacethylpyridinebis(benzoylhydrazone), H2DAPBH) in the different charge states (H2DAPBH0, HDAPBH1-, DAPBH2-) and various apical ligands (Cl-, CH3OH, SCN-) were synthesized and characterized structurally and magnetically: [V(H2DAPBH)Cl2]Cl·C2H5OH (1), [V(HDAPBH)(NCS)2]·0.5CH3CN·0.5CH3OH (2) and [V(DAPBH)(CH3OH)2]Cl·CH3OH (3). All three complexes reveal paramagnetic behavior, resulting from isolated S = 1 spins with positive zero-field splitting energy expected for the high-spin ground state of the V3+ (3d2) ion in a PBP coordination. Detailed high-field EPR measurements for compound 3 show that its magnetic properties are best described by using the spin Hamiltonian with the positive ZFS energy (D = +4.1 cm-1) and pronounced dimer-like antiferromagnetic spin coupling (J = -1.1 cm-1). Theoretical analysis based on superexchange calculations reveals that the long-range spin coupling between distant V3+ ions (8.65 Å) is mediated through π-stacking contacts between the planar DAPBH2- ligands of two neighboring [V(DAPBH)(CH3OH)2]+ complexes.