Electron-Driven Nitration of Unsaturated Hydrocarbons

Herein, we introduce an electrochemically assisted generation of nitryl radicals from ferric nitrate under mild reaction conditions using a simple setup with inexpensive graphite and stainless-steel electrodes. The mechanism of the reaction is supported by detailed spectroscopic and experimental studies. Powered by electricity and driven by electrons, the synthetic diversity of this reaction has been demonstrated through the development of highly efficient nitration protocols of various unsaturated hydrocarbons. In addition to a broad application area, these protocols are easy to scale for decagram quantities, and exhibit exceptional substrate generality and functional-group compatibility.     

Transformation of an Imine Cage to a Covalent Organic Framework Film at the Liquid–Liquid Interface

Dynamic covalent chemistry (DCC) opens up a fascinating route for the construction of well-organized supramolecular architectures, starting from organic molecular cages to crystalline macromolecular covalent organic frameworks (COFs). Herein, for the first time, we have manifested a facile room-temperature DCC-directed transformation of discrete organic imine cage-to-COF film at the liquid–liquid interface. The unfolding of the cage leading to the generation of imine intermediates, followed by their interface-assisted preorganization and subsequent growth of the COF film, are elucidated through detailed spectroscopic and microscopic investigations. The interfacial cage-to-COF transformation provides a facile route for the faster fabrication of free-standing COF films with high porosity and crystallinity, demonstrating excellent performance towards molecular sieving and high solvent permeance. Thus, the current study opens up a new route for structural interconversion between two crystalline entities with diverse dimensionality employing DCC at the confined interface.     

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.     

UV-to-NIR Harvesting Conjugated Porous Polymer Nanocomposite: Upconversion and Plasmon Expedited Thioether Photooxidation

Photocatalysts capable of harvesting a broad range of the solar spectrum are essential for sustainable chemical transformations and environmental remediation. Herein, we have integrated NIR-absorbing upconversion nanoparticles (UCNP) with UV-Vis absorbing conjugated porous organic polymer (POP) through the in situ multicomponent C−C coupling to fabricate a UC−POP nanocomposite. The light-harvesting ability of UC−POP is further augmented by loading plasmonic gold nanoparticles (AuNP) into UC−POP. A three-times enhancement in the upconversion luminescence is observed upon the incorporation of AuNP in UC−POP, subsequently boosting the photocatalytic activity of UC−POP−Au. The spectroscopic and photoelectrochemical investigations infer the enhanced photocatalytic oxidation of thioethers, including mustard gas simulant by UC−POP−Au compared to POP and UC−POP due to the facile electron-hole pair generation, suppressed exciton recombination, and efficient charge carrier migration. Thus, the unique design strategy of combining plasmonic and upconversion nanoparticles with a conjugated porous organic polymer opens up new vistas towards artificial light harvesting.