Organocatalytic Enantioselective Synthesis of Inherently Chiral Calix[4]arenes.

Inherently chiral calix[4]arenes are an excellent structural scaffold for enantioselective synthesis, chiral recognition, sensing, and circularly polarized luminescence. However, their catalytic enantioselective synthesis remains challenging. Herein, we report an efficient synthesis of inherently chiral calix[4]arene derivatives via cascade enantioselective cyclization and oxidation reactions. The three-component reaction features a broad substrate scope (33 examples), high efficiency (up to 90 % yield), and excellent enantioselectivity (>95 % ee on average). The potential applications of calix[4]arene derivatives are highlighted by their synthetic transformation and a detailed investigation of their photophysical and chiroptical properties.

A supramolecular artificial light-harvesting system based on a luminescent platinum(II) metallacage.

A trigonal luminescent metallacage was constructed by the coordination-driven self-assembly of m-pyridine-modified tetraphenylene ligands with organic Pt(II) acceptors, which exhibited excellent Aggregation-Induced Emission (AIE) properties. An efficient artificial light-harvesting system was successfully constructed by selecting the metallacage as the donor and the hydrophobic fluorescent dye Nile Red (NiR) as the donor molecule in a system of acetone/water (1/9, v/v), The absorption spectra of NiR and the emission spectra of the metallacage showed considerable overlap, achieving energy transfer from the metallacage to NiR.

Understanding of the Intrinsic Difference between n- and p-Doping Propagation in Polymer Light-Emitting Electrochemical Cells: A Numerical Modeling Approach.

Distinct doping propagation characteristics between p-doping and n-doping in light-emitting electrochemical cells (LECs) have been highlighted by intensive reports. Typically, there are significant differences in the doping speeds between p-doping and n-doping, with the former exhibiting a sawtooth frontier and the latter displaying a more uniform frontier profile. In addition, experimental observations demonstrate a uniform motion instead of the theoretically suggested accelerated electrochemical doping frontier propagation. Therefore, there is an urgent need to establish a quantitative model that delves into the underlying mechanisms responsible for doping propagation in LECs. In this study, four variables were selected to investigate the detailed mechanism of electrochemical doping propagation: temperature, voltage, and concentrations of salt and solid electrolyte. Fluorescence imaging revealed that the n-doping and p-doping propagations behaved contrarily with increasing temperature and voltage. By numerically fitting the doping propagation frontier, equations were derived to describe the relationship between the speed of electrochemical doping propagation and temperature/voltage. The underlying mechanisms were elucidated, indicating that anions undergo motion through the cooperative effects of electric field drift and concentration diffusion, while cation transport strongly relies on poly(ethylene oxide) (PEO) segmental motions. In other words, the movement of anions within the electrolyte is characterized by a greater degree of freedom, whereas the motion of cations is significantly dependent on the segmental motions of PEO. The resulting equations were well-fitted with experimental data, providing a solid foundation for further theoretical investigations into electrochemical doping in various devices.