Triindolo-Truxene Derivatives: Design, Synthesis, and Fine-Tuning of Electronic Properties and Molecular Assembly through Molecular Engineering.

Triindolo-truxene, a C3 -symmetric molecule with a large π-conjugated plane, has six methylene carbon atoms and three aromatic carbon atoms that can be facilely functionalized. Herein, butyl, carbonyl, cyano, and/or malononitrile groups were introduced at six methylene carbon atoms (6-, 14-, 22- or 8-, 16-, 24-positions) and/or three aromatic carbon atoms (2-, 10-, and 18-positions) of triindolo-truxene to produce eight derivatives. Their photophysical properties, electrochemical properties, and molecular assembly can be effectively modulated by substituents and substitution patterns. Incorporation of electron-deficient groups led to redshifts in both the absorption and emission of these derivatives and also lowered their HOMO and LUMO levels. Different substitution patterns resulted in the different intramolecular donor-acceptor interactions. Electron-deficient substituents at the methylene carbon atoms in the 6-, 14-, and 22-positions led to intramolecular charge transfer from the fluorene arms to the truxene core, whereas the corresponding substitutions at the methylene carbon atoms in the 8-, 16-, and 24-positions resulted in intramolecular charge transfer from the truxene core to the fluorene arms. The molecular packing in single crystals and molecular aggregation in solution are also influenced by the substituents and substitution patterns. This work provides a straightforward strategy to alter the properties of triindolo-truxene.

Interplay between magnetocrystalline anisotropy and exchange bias in epitaxial CoO/Co films.

The interplay between magnetocrystalline anisotropy and exchange bias is investigated in CoO/Co bilayer films, which are grown epitaxially on MgO (0 0 1), by magnetization reversal measurements based on the anisotropic magnetoresistance (AMR) effect. While an asymmetric magnetization reversal survives after training for cooling field (CF) along the hard axis, the magnetization reversal becomes symmetric and is dominated in both branches of the hysteresis loop by domain wall motion before and after training for CF along the easy axis. When performing an in-plane hysteresis loop perpendicular to the CF, the hysteresis loop along the easy axis becomes asymmetric: magnetization rotation dominates in the ascending branch, while there is a larger contribution of domain wall motion in the descending branch. Furthermore, the azimuthal angular dependence of the AMR shows two minima after performing a perpendicular hysteresis loop, instead of only one minimum after training. Relying on the extended Fulcomer and Charap model, these effects can be related to an increased deviation of the average uncompensated antiferromagnetic magnetization from the CF direction. This model provides a consistent interpretation of training and asymmetry of the magnetization reversal for epitaxial films with pronounced magnetocrystalline anisotropy as well as for the previously investigated polycrystalline films.

Exceeding natural resonance frequency limit of monodisperse Fe(3)O(4) nanoparticles via superparamagnetic relaxation.

Magnetic nanoparticles have attracted much research interest in the past decades due to their potential applications in microwave devices. Here, we adopted a novel technique to tune cut-off frequency exceeding the natural resonance frequency limit of monodisperse Fe3O4 nanoparticles via superparamagnetic relaxation. We observed that the cut-off frequency can be enhanced from 5.3 GHz for Fe3O4 to 6.9 GHz forFe3O4@SiO2 core-shell structure superparamagnetic nanoparticles, which are much higher than the natural resonance frequency of 1.3 GHz for Fe3O4 bulk material. This finding not only provides us a new approach to enhance the resonance frequency beyond the Snoek's limit, but also extend the application for superparamagnetic nanoparticles to microwave devices.

Determination of magnetic anisotropy constants in Fe ultrathin film on vicinal Si(111) by anisotropic magnetoresistance.

The epitaxial growth of ultrathin Fe film on Si(111) surface provides an excellent opportunity to investigate the contribution of magnetic anisotropy to magnetic behavior. Here, we present the anisotropic magnetoresistance (AMR) effect of Fe single crystal film on vicinal Si(111) substrate with atomically flat ultrathin p(2 × 2) iron silicide as buffer layer. Owing to the tiny misorientation from Fe(111) plane, the symmetry of magnetocrystalline anisotropy energy changes from the six-fold to a superposition of six-fold, four-fold and a weakly uniaxial contribution. Furthermore, the magnitudes of various magnetic anisotropy constants were derived from torque curves on the basis of AMR results. Our work suggests that AMR measurements can be employed to figure out precisely the contributions of various magnetic anisotropy constants.

Tuning magnetic anisotropies of Fe films on Si(111) substrate via direction variation of heating current.

We adopted a novel method to tune the terrace width of Si(111) substrate by varying the direction of heating current. It was observed that the uniaxial magnetic anisotropy (UMA) of Fe films grown on the Si(111) substrate enhanced with decreasing the terrace width and superimposed on the weak six-fold magnetocrystalline anisotropy. Furthermore, on the basis of the scanning tunneling microscopy (STM) images, self-correlation function calculations confirmed that the UMA was attributed mainly from the long-range dipolar interaction between the spins on the surface. Our work opens a new avenue to manipulate the magnetic anisotropy of magnetic structures on the stepped substrate by the decoration of its atomic steps.

Improvement of the uniformity and dipole ferromagnetism in Co nanodots assemblies on Pb/Si(111) via step tuned dimensionality variation.

We fabricated quasi-one-dimensional Co nanochain assemblies and two-dimensional Co nanodot assemblies on Pb/Si(111) substrates by step decoration. The morphology and magnetic properties of these two kinds of Co nanodot assemblies were investigated by in situ scanning tunneling microscopy and magneto-optical Kerr effect measurements. It was found that the steps cannot only improve the uniformity of the Co nanodots, but also increase the critical temperature T(c). Monte Carlo simulation indicates that the ferromagnetism mainly originates from the dipolar interactions and the critical temperature T(c) can be enhanced by introducing an in-plane uniaxial magnetic anisotropy via the step tuned dimensionality variation of the nanodot assemblies.