Magnetization Process of the S=1 and 1/2 Uniform and Distorted Kagome Heisenberg Antiferromagnets

The magnetization process of the S=1 and 1/2 kagome Heisenberg antiferromagnet is studied by means of the numerical exact diagonalization method. It is found that the magnetization curve at zero temperature has a plateau at 1/3 of the full magnetization. In the presence of $\sqrt{3} \times \sqrt{3}$ lattice distortion, this plateau is enhanced and eventually the ferrimagnetic state is realized. There also appear the minor plateaux above the main plateau. The physical origin of these phenomena is discussed.Comment: 5 pages, 10 figures included, to be published in J. Phys. Soc. Jp

Effect of fluorination on the crystal and electronic structure of organometallic cyclopentadienyl-phenylenediamino-cobalt complexes

The fluorinated half sandwich complex [CpCoLF] (Cp = cyclopentadiene; LF = o-perfluoro-phenylenediimine; 2F) shows a T-shaped geometry with the LF ligand coplanar with the metallocycle. The molecules are dimerized in a head-to-tail fashion and arranged in a herringbone manner in the crystal packing. The crystal structure of 2F is different from that of the corresponding hydrocarbon compound (2H). Moreover, the differences due to the presence of fluorine atoms are also highlighted by the analysis of the intermolecular contacts, which show that 2F exhibits several F⋯F contacts, as well as aromatic intra-dimer π … π interactions in addition to C–H … π and C–H⋯F contacts. No relevant π … π interactions are observed in the case of 2H. Hirshfeld Surface (HS) analysis also depicted well the differences in the solid state interactions between the different crystal structures. In particular, HS has been useful in highlighting the differences observed between the crystal structure of 2H obtained from Rietveld refinement and that measured on single crystal (2HP and 2HSCH, respectively). The effect of the fluorination on the electronic structure has been investigated also by CV measurements and Density Functional Theory calculations. Both are consistent with a lowering in energy of the molecular orbitals. Data Mining Force Field calculations clearly indicate that the 2HSCH structure is more stable than the 2HP one. These findings can be explained in terms of the energy of the intermolecular interactions. The enhanced stability of the fluorine substitute can be easily explained by the large number of strong interactions involving fluorine atoms

Potential modulations in flatland near infrared sensitization of MoS2 phototransistors by a solvatochromic dye directly tethered to sulfur vacancies

Near-infrared sensitization of monolayer MoS2 is here achieved via the covalent attachment of a novel heteroleptic nickel bis-dithiolene complex into sulfur vacancies in the MoS2 structure. Photocurrent action spectroscopy of the sensitized films reveals a discreet contribution from the sensitizer dye centred around 1300 nm (0.95 eV), well below the bandgap of MoS2 (2.1 eV), corresponding to the excitation of the monoanionic dithiolene complex. A mechanism of conductivity enhancement is proposed based on a photo-induced flattening of the corrugated energy landscape present at sulfur vacancy defect sites within the MoS2 due to a dipole change within the dye molecule upon photoexcitation. This method of sensitization might be readily extended to other functional molecules that can impart a change to the dielectric environment at the MoS2 surface under stimulation, thereby extending the breadth of detector applications for MoS2 and other transition metal dichalcogenides

Pressure induced enhancement of the magnetic ordering temperature in rhenium(IV) monomers

Materials that demonstrate long-range magnetic order are synonymous with information storage and the electronics industry, with the phenomenon commonly associated with metals, metal alloys or metal oxides and sulfides. A lesser known family of magnetically ordered complexes are the monometallic compounds of highly anisotropic d-block transition metals; the ‘transformation’ from isolated zero-dimensional molecule to ordered, spin-canted, three-dimensional lattice being the result of through-space interactions arising from the combination of large magnetic anisotropy and spin-delocalization from metal to ligand which induces important intermolecular contacts. Here we report the effect of pressure on two such mononuclear rhenium(IV) compounds that exhibit long-range magnetic order under ambient conditions via a spin canting mechanism, with Tc controlled by the strength of the intermolecular interactions. As these are determined by intermolecular distance, ‘squeezing’ the molecules closer together generates remarkable enhancements in ordering temperatures, with a linear dependence of Tc with pressure

Templating effects of tetrakis(thiadiazole) porphyrazine on the structure and optical properties of copper phthalocyanine thin films

Molecular templating is an attractive method to improve the crystallinity and control the molecular orientations of organic thin films. Here, we report on the templating effects of an organic nn-type semiconductor, tetrakis(thiadiazole)porphyrazine (H2TTDPz), on the structure and optical absorption of a pp-type semiconductor, copper phthalocyanine (CuPc). X-ray diffraction measurements for the double layer thin films, CuPc/H2TTDPz, indicate a face-on orientation of CuPc, which is replicating the structure of the H2TTDPz thin films, even though the CuPc thin films usually form edge-on-type thin films. The optical absorption measurements show new low-energy transitions in the templated CuPc films