Changhyun Koo

Single-Molecule-Magnet Behavior and Spin Changes Affected by Crystal Packing Effects

Five Mn 3Zn 2 heterometallic complexes have been synthesized and structurally and magnetically characterized. Spin ground states up to S = 6 have been observed for these complexes and are shown to depend on the cocrystallizing cation and on the terminal ligand. Large axial zero-field interactions ( D = -1.16 K) are the result of near-parallel alignment of the Mn (III) Jahn-Teller axes. High-frequency electron paramagnetic resonance, single-crystal magnetization hysteresis, and alternating current susceptibility measurements are presented to characterize [NEt 4] 3[Mn 3Zn 2(salox) 3O(N 3) 6X 2] [X (-) = Cl (-) ( 1), Br (-) ( 2)] and [AsPh 4] 3[Mn 3Zn 2(salox) 3O(N 3) 6Cl 2] ( 3) and reveal that 1 and 2 are single-molecule magnets ( U eff = 44 K), while 3 is not.

Heterometallic Integer-Spin Analogues of S ) 9 /2 Mn4 Cubane Single-Molecule Magnets

A family of distorted heterometallic cubanes, [Mn (III) 3Ni (II)(hmp) 3O(N 3) 3(O 2CR) 3], where O 2CR (-) is benzoate ( 1), 3-phenylpropionate ( 2), 1-adamantanecarboxylate ( 3), or acetate ( 4) and hmp (-) is the anion of 2-pyridinemethanol, was synthesized and structurally as well as magnetically characterized. These complexes have a distorted-cubane core structure similar to that found in the S = 9/2 Mn 4 cubane family of complexes. Complexes 1, 3, and 4 crystallize in rhombohedral, hexagonal, and cubic space groups, respectively, and have C 3 molecular symmetry, while complex 2 crystallizes in the monoclinic space group Cc with local C 1 symmetry. Magnetic susceptibility and magnetization hysteresis measurements and high-frequency electron paramagnetic resonance (HFEPR) spectroscopy established that complexes 1-4 have S = 5 spin ground states with axial zero-field splitting (ZFS) parameters ( D) ranging from -0.20 to -0.33 cm (-1). Magnetization versus direct-current field sweeps below 1.1 K revealed hysteresis loops with magnetization relaxation, definitely indicating that complexes 1-4 are single-molecule magnets that exhibit quantum tunneling of magnetization (QTM) through an anisotropy barrier. Complex 2 exhibits the smallest coercive field and fastest magnetization tunneling rate, suggesting a significant rhombic ZFS parameter ( E), as expected from the low C 1 symmetry. This was confirmed by HFEPR spectroscopy studies on single crystals that gave the following parameter values for complex 2: gz = 1.98, gx = gy = 1.95, D = -0.17 cm (-1), B 4 (0) = -6.68 x 10 (-5) cm (-1), E = 6.68 x 10 (-3) cm (-1), and B 4 (2) = -1.00 x 10 (-4) cm (-1). Single-crystal HFEPR data for complex 1 gave g z = 2.02, gx = gy = 1.95, D = -0.23 cm (-1), and B 4 (0) = -5.68 x 10 (-5) cm (-1), in keeping with the C 3 site symmetry of this Mn 3Ni complex. The combined results highlight the importance of spin-parity effects and molecular symmetry, which determine the QTM rates.

A new LiCoPO4 polymorph via low temperature synthesis

Non-olivine LiCoPO4 microcrystals have been synthesized at low temperatures by microwave-assisted hydrothermal synthesis. The resulting octahedra-like micrometer-sized crystals exhibit a Pn21a symmetry and are isostructural to LiZnPO4. The orthorhombic lattice constants are a = 10.023(8) A, b = 6.724(7) A, and c = 4.963(4) A. The microcrystals are metastable and transform to olivine LiCoPO4 upon heating above T ≈ 220 °C under an argon atmosphere. The magnetic properties confirm a phase pure material with a Co-valence of 2+, and imply long-range antiferromagnetic ordering below TN = 11 K. Electrochemical analysis by means of cyclic voltammetry displays a reversible redox couple at around 5.1 V/4.8 V vs. Li/Li+.

Magnetic Interactions in a Series of Homodinuclear Lanthanide Complexes.

A series of seven isostructural homodinuclear lanthanide complexes are reported. The magnetic properties (ac and dc SQUID measurements) are discussed on the basis of the X-ray structural properties which show that the two lanthanide sites are structurally different. MCD spectroscopy of the dysprosium(III) and neodymium(III) complexes ([Dy(III)2(L)(OAc)4](+) and [Nd(III)2(L)(OAc)4](+)) allowed us to thoroughly analyze the ligand field, and high-frequency EPR spectroscopy of the gadolinium(III) species ([Gd(III)2(L)(OAc)4](+)) showed the importance of dipolar coupling in these systems. An extensive quantum-chemical analysis of the dysprosium(III) complex ([Dy(III)2(L)(OAc)4](+)), involving an ab initio (CASSCF) wave function, explicit spin-orbit coupling (RASSI-SO), and a ligand field analysis (Lines model and Stevens operators), is in full agreement with all experimental data (SQUID, HF-EPR, MCD) and specifically allowed us to accurately simulate the experimental χT versus T data, which therefore allowed us to establish a qualitative model for all relaxation pathways.

Synthesis, magnetism, and high-frequency EPR spectroscopy of a family of mixed-valent cuboctahedral Mn13 complexes with 1,8-naphthalenedicarboxylate ligands.

Four mixed-valent (Mn(IV)Mn(III)(6)Mn(II)(6)) tridecanuclear Mn clusters [Mn(13)O(8)(OH)(6)(ndc)(6)] (1), [Mn(13)O(8)(OEt)(5)(OH)(ndc)(6)] (2), [Mn(13)O(8)(O(2)CPh)(12)(OEt)(6)] (3), and [Mn(13)O(8)(OMe)(6)(ndc)(6)] (4) are reported, where ndcH(2) is 1,8-naphthalenedicarboxylic acid. This is the first use of the latter in Mn chemistry. Complexes 1-3 are essentially isostructural and possess a central core composed of three layers. The middle layer consists of a Mn(II)(6) hexagon containing a central Mn(IV) atom, and above and below this are Mn(III)(3) triangular units. These core Mn atoms are held together by a combination of O(2-), RO(-), or HO(-) bridging groups. The overall metal topology is an unusual one, with the overall geometry being a metal-centered cuboctahedron (heptaparallelohedron). Variable-temperature, solid-state dc, and ac magnetization studies were carried out on complexes 1-4 in the 5.0-300 K range. Compound 1 was found to possess an S = 9/2 ground-state spin, whereas 2, 3, and 4 have an S = 11/2 ground state. Fitting of the magnetization (M) versus field (H) and temperature (T) data by matrix diagonalization and including only axial zero-field splitting, D, gave D = -0.14 cm(-1) for 1. High-frequency EPR studies were carried out on single crystals of 1.xDMF, and these confirmed D to be very small, that is, 1 is essentially isotropic. The combined work demonstrates the ligating ability of 1,8-naphthalenedicarboxylate, notwithstanding its robust organic backbone and the restricted parallel disposition of its two carboxylate moieties, and its usefulness in the synthesis of new polynuclear Mn(x) clusters. The work also demonstrates a sensitivity of the ground-state spin in this Mn(13) family of complexes to relatively small structural perturbations, while the high-frequency EPR study demonstrated the magnetically isotropic nature of the Mn(13) core.

A Three-Pronged Attack To Investigate the Electronic Structure of a Family of Ferromagnetic Fe4Ln2 Cyclic Coordination Clusters: A Combined Magnetic Susceptibility, High-Field/High-Frequency Electron Paramagnetic Resonance, and 57Fe Mössbauer Study

We present the synthesis, structure, magnetic properties, as well as the Mössbauer and electron paramagnetic resonance studies of a ring-shaped [FeIII4LnIII2(Htea)4(μ-N3)4(N3)3(piv)3] (Ln = Y 1, Gd 2, Tb 3, Dy 4, Ho 5, Er, 6) coordination cluster. The Dy, Tb, and Ho analogues show blocking of the magnetization at low temperatures without applied fields. The anisotropy of the 3d ion and the exchange interaction between 3d and 4f ions in Fe4Ln2 complexes are unambiguously determined by high-field/high-frequency electron paramagnetic resonance measurements at low temperature. Ferromagnetic exchange interaction JFe-Ln is found which decreases upon variation of the Ln ions to larger atomic numbers. This dependence is similar to the behavior shown in the effective barrier values of complexes 3-5. Further information about the anisotropy of the Ln3+ ions was gathered with 57Fe Mössbauer spectroscopy, and the combination of these methods provides detailed information regarding the electronic structure of these complexes.

New phase of MnSb2O6 prepared by ion exchange: structural, magnetic, and thermodynamic properties.

A new layered trigonal (P3̅1m) form of MnSb2O6, isostructural with MSb2O6 (M = Cd, Ca, Sr, Pb, and Ba) and MAs2O6 (M = Mn, Co, Ni, and Pd), was prepared by ion-exchange reaction between ilmenite-type NaSbO3 and MnSO4-KCl-KBr melt at 470 °C. It is characterized by Rietveld analysis of the X-ray diffraction pattern, electron microprobe analysis, magnetic susceptibility, specific heat, and ESR measurements as well as by density functional theory calculations. MnSb2O6 is very similar to MnAs2O6 in the temperature dependence of their magnetic susceptibility and spin exchange interactions. The magnetic susceptibility and specific heat data show that MnSb2O6 undergoes a long-range antiferromagnetic order with Néel temperature TN = 8.5(5) K. In addition, a weak ferromagnetic component appears below T1 = 41.5(5) K. DFT+U implies that the main spin exchange interactions are antiferromagnetic, thereby forming spin-frustrated triangles. The long-range ordered magnetic structure of MnSb2O6 is predicted to be incommensurate as found for MnAs2O6. On heating, the new phase transforms to the stable P321 form via its intermediate disordered variant.

Magnetic anisotropy and the phase diagram of chiral MnSb2O6

The magnetic phase diagram and low-energy magnon excitations of structurally and magnetically chiral MnSb2O6 are reported. The specific heat and the static magnetization are investigated in magnetic fields up to 9 and 30 T, respectively, while the dynamicmagnetic properties are probed by X-band as well as tunable high-frequency electron spin-resonance spectroscopy. Below TN = 11.5 K, we observe antiferromagnetic resonance modes which imply small but finite planar anisotropy showing up in a zero-field splitting of 20 GHz. The data are well described by means of an easy-plane two-sublattice model with the anisotropy field BA = 0.02 T. The exchange field BE = 13 T is obtained from the saturation field derived from the pulsed-field magnetization. A crucial role of the small anisotropy for the spin structure is reflected by competing antiferromagnetic phases appearing, at T = 2 K, in small magnetic fields at BC1

Anisotropy-governed competition of magnetic phases in the honeycomb quantum magnet Na3Ni2SbO6 studied by dilatometry and high-frequency ESR

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Static and Dynamic Magnetic Response of Fragmented Haldane-like Spin Chains in Layered Li3Cu2SbO6

0.5 T and BC2 = 0.9 T. We discuss the results in terms of spin reorientation and of small magnetic fields favoring helical spin structure over the cycloidal ground state which, at B = 0, is stabilized by the planar anisotropy. Above TN, short-range magnetic correlations up to >=60 K and magnetic entropy changes well above TN reflect the frustrated triangular arrangement of Mn2+ ions in MnSb2O6.