A Molecular Photosensitizer in a Porous Block Copolymer Matrix-Implications for the Design of Photocatalytically Active Membranes

Recently, porous photocatalytically active block copolymer membranes were introduced, based on heterogenized molecular catalysts. Here, we report the integration of the photosensitizer, i. e., the light absorbing unit in an intermolecular photocatalytic system into block copolymer membranes in a covalent manner. We study the resulting structure and evaluate the orientational mobility of the photosensitizer as integral part of the photocatalytic system in such membranes. To this end we utilize transient absorption anisotropy, highlighting the temporal reorientation of the transition dipole moment probed in a femtosecond pump-probe experiment. Our findings indicate that the photosensitizer is rigidly bound to the polymer membrane and shows a large heterogeneity of absolute anisotropy values as a function of location probed within the matrix. This reflects the sample inhomogeneity arising from different protonation states of the photosensitizer and different intermolecular interactions of the photosensitizers within the block copolymer membrane scaffold.     

Ferrimagnetic behaviors in a double-wall cubic metal nanotube

A double-wall cubic metal nanotube consists of the ferromagnetic spin-1 inner shell and spin-3/2 surface shell. It is of the ferrimagnetic exchange coupling between two shells. Considering the single-ion anisotropy and transverse field exist together, the magnetization, the initial susceptibility, the internal energy and the specific heat have been investigated by using the effective-field theory with correlations. Some interesting phenomena have been found in the thermal variations of the system. Magnetization appears two or three compensation points in certain parameters. It is an unconventional ferrimagnetic behavior in the nanotube. The shapes of total magnetization and the initial susceptibility are great influenced by the surface exchange coupling, surface single-ion anisotropy and surface transverse field. Some results of nanotube may have potential applications in different research fields, such as electronics, optics, mechanics, and even biomedicine and molecular devices.     

Unravelling the Relationship between Raman Enhancement and Photocatalytic Activity on Single Anisotropic Au Microplates

Anisotropic noble‐metal structures are attracting increasing attention because of interesting size‐ and shape‐dependent properties and have emerging applications in the fields of optics and catalysis. However, it remains a significant challenge to overcome chemical contributions and acquire molecular insight into the relationship between Raman enhancement and photocatalytic activity. This study gives visualized experimental evidence of the anisotropic spatial distribution of Raman signals and photocatalytic activity at the level of single nanometer‐thin Au microtriangles and microhexagons. Theoretical simulations indicate an anisotropic spatial distribution and sharpness‐dependent strength of the electric‐field enhancement. Analysis by using statistical surface‐enhanced Raman scattering (SERS) supports this view, that is, Raman enhancement is on the order of corner>edge>face for a single microplate, but SERS measurements at different depths of focus also imply a concentration‐dependent feature of SERS signals, especially at the corners and edges. Similarly, the SERS signals of product molecules in plasmonic photocatalysis also exhibit asymmetrical strengths at different corners of the same microplate. However, by examining the variations in the relative intensities of the SERS peaks, the difference in the photocatalytic activities at the corners, edges, and faces has been successfully calculated and is highly consistent with electric‐field simulations, thus indicating that an increased number of molecules adsorbed at specific sites does not necessarily lead to a higher conversion ratio in noble‐metal photocatalysis. Our strategy weakens the assumed impact of plasmonic local heating and, to a certain extent, excludes the influence of concentration effects and chemical contributions in noble‐metal photocatalysis, thus clearly profiling plasmon‐related characteristics. This study also promises a new research direction to understand the enhancement mechanism of SERS‐active structures.     

Photoresponding ionic complex containing azobenzene chromophore for use in birefringent flm简

A novel photoresponding ionic complex （PANDAZO） was prepared by the ionic self-assembly （1SA） of sodium polyacrylate （PANa） and azobenzene chromophores （NDAZO）. The ionic complex forms an interdigitated lamellar structure with full overlap of the side chains. The optical anisotropy was investigated by using a polarization pulse laser （355 nm）. Furthermore, a high photoinduced birefringence （An = 0.365） was measured by using a continuous 488 nm laser as the pump light.     

Mononuclear High-spin Octahedral Cobalt(II) Complex with Positive Axial Magnetic Anisotropy: Synthesis,Crystal Structure,and DFT Studies

This article outlines the magnetic features of a new six–coordinate high-spin cobalt(II) complex cis-[Co^II(tmphen)₂(NCS)₂] ( 1 ) achieved via the reactions of cobalt(II) thiocyanate with 3,4,7,8-tetramethyl-1,10-phenanthroline. The complex 1 was thoroughly characterized by different analytical and spectroscopic techniques and further confirmed by single X-ray crystal diffraction pattern. Complex 1 is a neutral molecule and adopt highly distorted six-coordinate CoN₆ octahedral coordination sphere surrounded by two thiocyanate N atoms in cis locations and the equatorial plane is occupied by two imine N atoms from the two tmphen ligand while the remaining two imine N atoms reside in the axial positions. Magnetic susceptibility data of complex 1 revealed that the χ_ΜT values decrease significantly to a value of 1.49 cm³ · K · mol^–1 at 2.0 K on decreasing temperatures below 100 K, mainly ascribed to the significant spin–orbit coupling (SOC) of six-coordinate Co^II ions. Furthermore, a field-dependence measurement was performed at 2 K, which shows a positive curvature up to 27 kOe, while it becomes linear up to 2.01 Nμ_B, which authenticated the fact that only the lowest Kramers doublet of ground state is appreciably populated.     

Probing Relaxation Dynamics in Five-Coordinate Dysprosium Single-Molecule Magnets

A new family of five-coordinate lanthanide single-molecule magnets (Ln SMMs) [Dy(Mes*O)₂(THF)₂X] (Mes*=2,4,6-tri-tert-butylphenyl; X=Cl, 1 ; Br, 2 ; I, 3 ) is reported with energy barriers to magnetic reversal >1200 K. The five-coordinate Dy^III ions have distorted square pyramidal geometries, with halide anions on the apex, and two Mes*O ligands mutually trans- to each other, and the two THF molecules forming the second trans- pair. These geometrical features lead to a large magnetic anisotropy in these complexes along the trans-Mes*O direction. QTM and Raman relaxation times are enhanced by varying the apex halide from Cl to Br to I, or by dilution in a diamagnetic yttrium analogue.     

Correlation between Ferromagnetic Layer Easy Axis and the Tilt Angle of Self Assembled Chiral Molecules

The spin–spin interactions between chiral molecules and ferromagnetic metals were found to be strongly affected by the chiral induced spin selectivity effect. Previous works unraveled two complementary phenomena: magnetization reorientation of ferromagnetic thin film upon adsorption of chiral molecules and different interaction rate of opposite enantiomers with a magnetic substrate. These phenomena were all observed when the easy axis of the ferromagnet was out of plane. In this work, the effects of the ferromagnetic easy axis direction, on both the chiral molecular monolayer tilt angle and the magnetization reorientation of the magnetic substrate, are studied using magnetic force microscopy. We have also studied the effect of an applied external magnetic field during the adsorption process. Our results show a clear correlation between the ferromagnetic layer easy axis direction and the tilt angle of the bonded molecules. This tilt angle was found to be larger for an in plane easy axis as compared to an out of plane easy axis. Adsorption under external magnetic field shows that magnetization reorientation occurs also after the adsorption event. These findings show that the interaction between chiral molecules and ferromagnetic layers stabilizes the magnetic reorientation, even after the adsorption, and strongly depends on the anisotropy of the magnetic substrate. This unique behavior is important for developing enantiomer separation techniques using magnetic substrates.     

Enantiomeric Discrimination by Surface‐Enhanced Raman Scattering–Chiral Anisotropy of Chiral Nanostructured Gold Films

A surface‐enhanced Raman scattering‐chiral anisotropy (SERS‐ChA) effect is reported that combines chiral discrimination and surface Raman scattering enhancement on chiral nanostructured Au films (CNAFs) equipped in the normal Raman scattering Spectrometer. The CNAFs provided remarkably higher enhancement factors of Raman scattering (EFs) for particular enantiomers, and the SERS intensity was proportional to the enantiomeric excesses (ee) values. Except for molecules with mesomeric species, all of the tested enantiomers exhibited high SERS‐ChA asymmetry factors (g), ranging between 1.34 and 1.99 regardless of polarities, sizes, chromophores, concentrations and ee. The effect might be attributed to selective resonance coupling between the induced electric and magnetic dipoles associated with enantiomers and chiral plasmonic modes of CNAFs.