Janus-Type AIE Fluorophores: Synthesis and Properties of π-Extended Coumarin-Bearing Triskelions

Janus-type triskelion-shaped fluorophores comprising coumarins bearing various electron-donating substituents (1aad, 1add, 1ccd, and 1cdd) were successfully synthesized via an intramolecular Ullmann coupling. Density functional theory (DFT) calculations indicated that all the compounds presented two different molecular surfaces, similar to Janus-type molecules. The absorption and fluorescence spectra of asymmetrical derivatives 1aad, 1add, 1ccd, and 1cdd exhibited a bathochromic shift due to their narrow highest occupied molecular orbital (HOMO) –lowest unoccupied molecular orbital (LUMO) gap. Natural transition orbital (NTO) analysis indicated that the excited state orbital overlaps differ among the C₃ symmetrical and asymmetrical dyes. These triskelion-shaped fluorophores were found to form molecular nanoaggregates in THF/H₂O mixtures and demonstrated aggregation-induced emission (AIE) enhancement characteristics as a result of restricting their molecular inversion. These results indicate that Janus-type AIE fluorophores are potentially applicable as solid-state fluorescent chiral materials, which can be optimized by controlling their molecular rearrangement in the solid state.     

Highly fluorescent M2L4 molecular capsules with anthracene shells

M(2)L(4) molecular capsules self-assembled from M(II) ions (where M = Zn, Ni, and Pd) and bent bidentate ligands constructed from anthracene fluorophores. The Ni(II) and Zn(II) capsules exhibited weak to strong blue emission unlike traditional Pd(II) cages and capsules.     

Quasi-Cyclic Codes from a Finite Affine Plane

Finite geometry codes are defined as the null spaces of the incidence matrices of points and flats in finite geometries. In this paper, we investigate the incidence matrix of points other than the origin and lines not passing through the origin in the affine plane AG(2,2^s), and we present two classes of quasi-cyclic codes derived from submatrices of the point-line incidence matrix. We also investigate the 2-ranks of those submatrices. AMS Classification: 94B25, 94B05     

Analysis of magnetic and structural phase transition behaviors of La1−xSrxCrO3 for preparation of phase diagram

The phase transition behavior of perovskite-type compounds, La_1−xSr_xCrO₃, was investigated by differential scanning calorimetry (DSC), dilatometry, dc magnetic susceptibility measurement and X-ray diffraction analysis. Both second-order magnetic phase transition from antiferromagnetic to paramagnetic and first-order structural phase transition from orthorhombic to rhombohedral were observed in the DSC or dilatometric curve of every specimen. The temperatures of both these magnetic and structural phase transitions decreased linearly with an increase in Sr content. The structural phase transition temperature of La_1−xSr_xCrO₃ with x less than 0.11 is higher than the magnetic phase transition temperature; however, a larger decrease in structural phase transition temperature than in magnetic phase transition temperature was observed with an increase in Sr content, resulting in a structural phase transition temperature lower than the magnetic phase transition temperature for La_1−xSr_xCrO₃ with x of more than 0.12. It was also observed that the heat of absorption of the structural phase transition decreased with an increase in x. In the dependence of dc magnetic susceptibility on temperature, variations by not only magnetic but also structural phase transitions were observed. It was also revealed that thermal expansion coefficient is affected not only by structural phase transition but also magnetic phase transition. Magnetic and structural phase diagram of La_1−xSr_xCrO₃, suggesting the existence of two Sr contents and temperatures at which triple phases coexist, was proposed.     

Crystal Engineering Approach To Design Colorimetric Indicator Array To Discriminate Positional Isomers of Aromatic Organic Molecules

Discriminating by color : A 2D colorimetric indicator array has been designed by a crystal engineering approach (N???H? O hydrogen bonding and charge‐transfer complexation) involving solid‐state co‐grinding for the visual discrimination of positional isomers of dihydroxynaphthalene. Factors governing the close packing of π planes, and hence color of the complex, were determined by single‐crystal X‐ray analysis, allowing fine tuning by crystal engineering.