The reaction of diethyl 2,5-bis(tert-butyl)phenoxy-3,6-dihydroxyterephthalate (1) with tetraethylene glycol di(p-toluenesulfonate) under high-dilution conditions afforded several isolated products. Two products were identified as macrocycles with one being the 1 + 1 crown ether derivative 3 (10% yield), and the second being the 2 + 2 crown ether compound D3 (19% yield). The X-ray structure for 3 was determined with the asymmetric unit observed to comprise half of the molecule. The small crown ether ring of 3 interacts with K+ or H+ ions in MeOH, but binding is weak and the macrocyclic cavity is too small to fully encapsulate the K+ ion. Transesterification of compounds 1, its methylated version 2 and 3 with diols such as ethylene glycol or 1,4-butandiol produced monomers (M1-M3) which were reacted with terephthaloyl chloride. Short oligomers were produced (PolyM1-PolyM3) rather than extensive polymeric materials and all displayed solid state fluorescence. The absorption and fluorescence properties of M1-M2 and their polymers can be related to subtle structural changes. The Stokes shift for M2 of 15 627 cm-1 in DCM is one of the largest observed for a simple organic chromophore in fluid solution.
Correction for 'Functionalized fluorescent terephthalate monomers and their attempted polyester formation' by Yvonne S. L. Choo et al., Org. Biomol. Chem., 2020, 18, 8735-8745, DOI: 10.1039/D0OB01533D.
The development of anion exchange membranes (AEMs) is hindered by the trade-off of ionic conductivity, alkaline stability, and mechanical properties. Tröger's base polymers (Tb-polymers) are recognized as promising membrane materials to overcome these obstacles. Herein, the AEMs made from Tb-poly(crown ether)s (Tb-PCEs) show good comprehensive performance. The influence of crown ether on the conductivity and alkaline stability of AEMs has been investigated in detail. The formation of hydronium ion-crown ether complexes and an obvious microphase-separated structure formed by the existence of crown ether can enhance the conductivity of the AEMs. The maximum OH- conductivity of 141.5 mS cm-1 is achieved from the Tb-PCEs based AEM (Tb-PCE-1) at 80 °C in ultrapure water. The ion-dipole interaction of the Na+ with crown ether can protect the quaternary ammonium from the attack of OH- to improve the alkaline stability of AEMs. After 675 h of alkaline treatment, the OH- conductivity of Tb-PCE-1 decreases by only 6%. The Tb-PCE-1-based single cell shows a peak power density of 0.202 W cm-2 at 80 °C. The prominent physicochemical properties are attributed to the well-developed microstructure of the Tb-PCEs, as revealed by TEM, AFM, and SAXS observations.
Anion exchange membrane fuel cells (AEMFCs) have emerged as a promising alternative to proton exchange membrane fuel cells (PEMFCs) due to their adaptability to low-cost stack components and non-noble-metals catalysts. However, the poor alkaline resistance and low OH- conductivity of anion exchange membranes (AEMs) have impeded the large-scale implementation of AEMFCs. Herein, the preparation of a new type of AEMs with crown ether macrocycles in their main chains via a one-pot superacid catalyzed reaction was reported. The study aimed to examine the influence of crown ether cavity size on the phase separation structure, ionic conductivity and alkali resistance of anion exchange membranes. Attributed to the self-assembly of crown ethers, the poly (crown ether) (PCE) AEMs with dibenzo-18-crown-6-ether (QAPCE-18-6) exhibit an obvious phase separated structure and a maximum OH- conductivity of 122.5 mS cm-1 at 80 °C (ionic exchange capacity is 1.51 meq g-1). QAPCE-18-6 shows a good alkali resistance with the OH- conductivity retention of 94.5% albeit being treated in a harsh alkali condition. Moreover, the hydrogen/oxygen single cell equipped with QAPCE-18-6 can achieve a peak power density (PPD) of 574 mW cm-2 at a current density of 1.39 A cm-2.
The concepts of sustainability and sustainable chemistry have attracted increasing attention in recent years, being of great importance to the younger generation. In this Viewpoint Article, we share how early-career chemists can contribute to the sustainable transformation of their discipline. We identify ways in which they can engage to catalyse action for change. This article does not attempt to answer questions about the most promising or pressing areas driving research and chemical innovation in the context of sustainability. Instead, we want to inspire and engage early-career chemists in pursuing sustainable actions by showcasing opportunities in education, outreach and policymaking, research culture and publishing, while highlighting existing challenges and the complexity of the topic. We want to empower early-career chemists by providing resources and ideas for engagement for a sustainable future globally. While the article focuses on students and early-career chemists, it provides insights to further stimulate the engagement of scientists from diverse backgrounds.