Copper‐mediated methods for the synthesis of perfluoroalkyl‐substituted corannulene derivatives have been developed, including long‐chain derivatives such as perfluorooctyl. The moderate to high yields of these mild and selective methods enable the production of sufficient amounts of material to conduct extensive electrochemical and photophysical measurements on a cognate series of compounds. The electrochemical measurements reproduce well previous measurements. The optical measurements display a constant set of electronic transitions across the series.

Covalent organic frameworks (COFs) are new organic porous materials constructed by covalent bonds, with the advantages of pre‐designable topology, adjustable pore size and abundant active sites. Many research studies have shown that COFs exhibit great potential in gas adsorption, molecular separation, catalysis, drug delivery, energy storage, etc. However, the electrons and holes of intrinsic COF are prone to compounding in transport, and the carrier lifetime is short. The donor‐acceptor (D−A) type COFs, which are synthesized by introducing D and A units into the COFs backbone, combine separated electron and hole migration pathway, tunable band gap and optoelectronic properties of D‐A type polymers with the unique advantages of COFs and have made great progress in related research in recent years. Here, the synthetic strategies of D−A type COFs are firstly outlined, including the rational design of linkages and D−A units as well as functionalization approaches. Then the applications of D−A type COFs in catalytic reactions, photothermal therapy and electronic materials are systematically summarized. In the final section, the current challenges, and new directions for the development of D−A type COFs are presented.This article is protected by copyright. All rights reserved

A novel Pd-catalysed C-H activation reaction for the synthesis of biaryl imino/keto carboxylic acids is developed. This reaction underwent aryl amide directed C-H activation ortho-acylation followed by ring closing and ring opening processes to give a range of biaryl imino/keto carboxylic acids. Our methodology features the utilization of a cheap and green oxidant (TBHP) as well as readily available aldehydes.

A series of conformationally rigid (Zn-salphen)2 complexes with a planar bridging component (xanthene or dibenzofuran) are described. Conformational changes for these assemblies are essentially limited to the axial rotation of the Zn-salphen moieties; however, such geometric constraints crucially permit the subtle tuning of the intermetallic separation and geometry to potentially enhance catalytic activity (and cooperative effects). The complexes have been investigated as catalysts in conjunction with n Bu4NI for the coupling of CO2 with epoxides. Selected dibenzofuran derivatives are significantly more active for the production of cyclic carbonate than their mononuclear analogues under identical conditions and concentrations of Zn sites. High initial turnover frequencies (up to 29 000 h–1; 14 500 h–1 per Zn, using 10 bar of CO2 at 95 °C) and excellent efficiencies under mild conditions (1 bar of CO2 at 55 °C) have been achieved. Kinetic studies using in situ (ReactIR) spectroscopy and density functional theory calculations have been performed, which reveal the existence of an intramolecular rate component and a preference for the cooperative pathway as well as transition states that depict the Zn sites operating in tandem. Taken together, these results provide strong evidence of cooperative reactivity in these Zn2 catalysts.