Effect of Fluorine Substitution on Absorption and Emission Properties of Figure-eight-shaped [5]Helicene Dimer: A Computational Study at RI-MP2/RI-ADC(2) Level

Chirality is a very important characteristic of optically active molecules and polyaromatics with helical structures, and plays a vital role in various applications in material science. In the present work, we show the effects of fluorine substitution at various positions in a figure-8-shaped [5]helicene dimer on the ground and excited state g-factors. Calculations for the ground and excited states are performed at the MP2 and ADC(2) levels of theory, respectively. The results reveal that fluorination has a large effect on the excited state structures. The values of the excited state dissymmetry factors for the molecules with fluorinations at both ends of the figure-8 systems are smaller than that of the parent system. On the other hand, fluorinations only in the stacked-phenyl region results in an increase in the value of . The perfluorinated system shows the smallest .     

Ligand-Mediated Revival of Degraded α-CsPbI3 to Stable Highly Luminescent Perovskite

Although α-CsPbI₃ is regarded as an attractive optical luminophore, it is readily degraded to the optically inactive δ-phase under ambient conditions. Here, we present a simple approach to revive degraded (“optically sick”) α-CsPbI₃ through “medication” with thiol-containing ligands. The effect of different types of thiols is systematically studied through optical spectroscopy. The structural reconstruction of degraded α-CsPbI₃ nanocrystals to cubic crystals in the presence of thiol-containing ligands is visualized through high-resolution transmission electron microscopy and supported by X-ray diffraction analysis. We found that 1-dodecanethiol (DSH) effectively revives degraded CsPbI₃ and results in high immunity towards moisture and oxygen, hitherto unreported. DSH facilitates the passivation of surface defects and etching of degraded Cs₄PbI₆ phase, thus reverting them back to the cubic CsPbI₃ phase, leading to enhanced PL and environmental stability.     

Visible-light-switchable Chalcone-Flavylium Photochromic Systems in Aqueous Media

The chalcone-flavylium photochromic system switches in aqueous media. However, the chalcone→flavylium conversion requires detrimental ultra-violet (UV) light for the switching which deters their applications in the biological domain. To address this issue, we have synthesized strategically modified chalcone scaffolds that can be reversibly switched to the flavylium forms with visible light ranging from 456 nm (blue) to 640 nm (red).     

Realization of Z2 Topological Metal in Single-Crystalline Nickel Deficient NiV2Se4

Temperature-dependent electronic and magnetic properties are reported for nickel-deficient NiV₂Se₄. Single-crystal X-ray diffraction shows it to crystallize in the monoclinic Cr₃S₄ structure type with space group $I2/m$ and vacancies on the Ni site, resulting in the composition Ni_0.85V₂Se₄ in agreement with our electron-probe microanalysis. Structural distortions are not observed down to 1.5 K. Nevertheless, the electrical resistivity shows metallic behavior with a broad anomaly around 150–200 K that is also observed in the heat capacity data. This anomaly indicates a change of state of the material below 150 K. It is believed that this anomaly could be due to spin fluctuations or charge-density-wave fluctuations, where the lack of long-range order is caused by vacancies at the Ni site of Ni_0.85V₂Se₄. The non-linear temperature dependence of the resistivity as well as an enhanced value of the Sommerfeld coefficient $\gamma =104.0(1)$ mJ mol⁻¹ K⁻² suggest strong electron–electron correlations in this material. First-principles calculations performed for NiV₂Se₄, which are also applicable to Ni_0.85V₂Se₄, classify this material as a topological metal with $Z_2=(1;110)$ and coexisting electron and hole pockets at the Fermi level. The phonon spectrum lacks any soft phonon mode, consistent with the absence of periodic lattice distortion in the present experiments.