Hiroyuki Nojiri

Polyoxometalate‐Mediated Self‐Assembly of Single‐Molecule Magnets: {[XW9O34]2[MnIII4MnII2O4(H2O)4]}12−

Last night of the POMs: The title compound (X=GeIV) exhibits slow relaxation of magnetization and quantum tunneling with a single-molecule magnetic behavior. Significant structural differences in the [MnIII4MnII2O4(H2O)4]8+ cluster core of the X=SiIV analogue modify the magnetic properties, thereby illustrating how polyoxometalate (POM) ligands can help in the systematic construction of nanoscale magnets.

Three-way switching in a cyanide-bridged [CoFe] chain

Bistable compounds that exist in two interchangeable phases under identical conditions can act as switches under external stimuli. Among such switchable materials, coordination complexes have energy levels (or phases) that are determined by the electronic states of their constituent metal ions and ligands. They can exhibit multiple bistabilities and hold promise in the search for multifaceted materials that display different properties in different phases, accessible through the application of contrasting external stimuli. Molecular systems that exhibit both thermo- and photoinduced magnetic bistabilities are excellent candidates for such systems. Here we describe a cyanide-bridged [CoFe] one-dimensional chiral coordination polymer that displays both magnetic and electric bistabilities in the same temperature range. Both the electric and magnetic switching probably arise from the same electron-transfer coupled spin-transition phenomenon, which enables the reversible conversion between an insulating diamagnetic phase and either a semiconducting paramagnetic (thermoinduced) or a type of ferromagnetic single-chain magnet (photoinduced) state.

TRANSITION BETWEEN TWO FERROMAGNETIC STATES DRIVEN BY ORBITAL ORDERING IN LA0.88SR0.12MNO3

A lightly doped perovskite mangantite La_{0.88}Sr_{0.12}MnO_3 exhibits a phase transition at T_{OO}=145 K from a ferromagnetic metal (T_C=172 K) to a novel ferromagnetic insulator.We identify that the key parameter in the transition is the orbital degree of freedom in e_g electrons. By utilizing the resonant x-ray scattering technique, orbital ordering is directly detected below T_{OO}, in spite of a significant diminution of the cooperative Jahn-Teller distortion. The new experimental features are well described by a theory treating the orbital degree of freedom under strong electron correlation. The present experimental and theoretical studies uncover a crucial role of the orbital degree in the metal-insulator transition in lightly doped manganites.

Direct observation of the multiple spin gap excitations in two-dimensional dimer system SrCu2(BO3)2

Various spin-gap excitations have been observed in the two-dimensional dimer system SrCu 2 (BO 3 ) 2 by ESR. The zero-field energy gap of the lowest spin-gap excitation shows a splitting into two triplet modes and the energy splitting clearly depends on the magnetic field orientation. A zero-field splitting is also found between the S z =+1 and S z =-1 branches of each triplet. These behaviors are qualitatively explained by considering the anisotropic inter-dimer and intra-dimer exchange couplings. The averaged value of the lowest spin-gap energy is determined to be 722±2 GHz (34.7 K). We have also found a second spin-gap excitation at 1140 GHz (54.7 K), which indicates that the inter-dimer coupling is strong. Besides these modes, a number of gapped ESR absorptions are found and we propose that these excitations are caused by the localized nature of the excited state in the present system.

Three-dimensional charge density wave order in YBa2Cu3O6.67 at high magnetic fields.

Discerning charge patterns in a cuprate Copper oxides are well known to be able to achieve the order required for superconductivity. They can also achieve another order—one that produces patterns in their charge density. Experiments using nuclear magnetic resonanceand resonant x-ray scattering have both detected this so-called charge density wave (CDW) in yttrium-based cuprates. However, the nature of the CDW appeared to be different in the two types of measurement. Gerber et al. used pulsed magnetic fields of up to 28 T, combined with scattering, to bridge the gap (see the Perspective by Julien). As the magnetic field increased, a two-dimensional CDW gave way to a three-dimensional one. Science, this issue p. 949; see also p. 914 X-ray scattering at high magnetic fields is used to probe charge density wave ordering in a cuprate. [Also see Perspective by Julien] Charge density wave (CDW) correlations have been shown to universally exist in cuprate superconductors. However, their nature at high fields inferred from nuclear magnetic resonance is distinct from that measured with x-ray scattering at zero and low fields. We combined a pulsed magnet with an x-ray free-electron laser to characterize the CDW in YBa2Cu3O6.67 via x-ray scattering in fields of up to 28 tesla. While the zero-field CDW order, which develops at temperatures below ~150 kelvin, is essentially two dimensional, at lower temperature and beyond 15 tesla, another three-dimensionally ordered CDW emerges. The field-induced CDW appears around the zero-field superconducting transition temperature; in contrast, the incommensurate in-plane ordering vector is field-independent. This implies that the two forms of CDW and high-temperature superconductivity are intimately linked.

Undecanuclear mixed-valence 3d–4f bimetallic clusters

Two undecanuclear 3d-4f clusters with the general formula {Mn(III)(4)Mn(IV)Ln(III)(6)}, where Ln = Gd or Tb, were synthesized, with both showing large spin ground states, and the Tb species acting as a single molecule magnet.

A ferromagnetically coupled Fe 42 cyanide-bridged nanocage

Self-assembly of artificial nanoscale units into superstructures is a prevalent topic in science. In biomimicry, scientists attempt to develop artificial self-assembled nanoarchitectures. However, despite extensive efforts, the preparation of nanoarchitectures with superior physical properties remains a challenge. For example, one of the major topics in the field of molecular magnetism is the development of high-spin (HS) molecules. Here, we report a cyanide-bridged magnetic nanocage composed of 18 HS iron(III) ions and 24 low-spin iron(II) ions. The magnetic iron(III) centres are ferromagnetically coupled, yielding the highest ground-state spin number (S=45) of any molecule reported to date.

Magnetic characterization of the frustrated three-leg ladder compound [(CuCl2tachH)3Cl]Cl2

We report the magnetic features of a one-dimensional stack of antiferromagnetically coupled equilateral copper(II) triangles. High-field magnetization measurements show that the interaction between the copper triangles is of the same order of magnitude as the intratriangle exchange although only coupled via hydrogen bonds. The infinite chain turns out to be an interesting example of a frustrated cylindrical three-leg ladder with competing intra- and inter-triangle interactions. We demonstrate that the ground state is a spin singlet which is gaped from the triplet excitation.

Directed assembly of nanoscale Co(II)-substituted {Co9[P2W15]3} and {Co14[P2W15]4} polyoxometalates

Herein we report two structurally intriguing Co(ii)-substituted polyoxometalates, a {Co(9)[P(2)W(15)](3)} and {Co(14)[P(2)W(15)](4)} (compounds 1 and 2) that are formed from the same building blocks under subtly different conditions. Compound 1 displays a structure previously predicted but never before realised, whilst compound 2 is the first Co-containing Dawson-based single-molecule magnet and has a unique cruciform structure.

Linear trinuclear Zn(II)-Ce(III)-Zn(II) complex which behaves as a single-molecule magnet.

Linear Zn(II)-Ce(III)-Zn(II) complex, which involves only one 4f electron as a spin source, behaves as an SMM. Easy-axis magnetic anisotropy for the ground (2)F(5/2) state of Ce(III) was achieved by a uni-axial crystal field, which is formed with four phenoxo oxygens as axial donors with the other five oxygens as equatorial donors.