Hydrogen‐Bonding Catalysis of Alkyl‐Onium Salts

The synthetic utility of alkyl‐onium salt compounds is widely recognized in the field of organic chemistry. Among the wide variety of onium salts, quaternary ammonium, phosphonium, and tertiary sulfonium salts have been the most useful compounds in organic syntheses. These compounds have been very useful reagents in the construction of organic building blocks. In addition, onium salts are known as reliable catalysts, which are used to promote important organic transformations by serving as phase‐transfer and ion‐pair catalysts through the activation of nucleophiles. Although phase‐transfer catalysis is a major direction for onium salt catalysis, hydrogen‐bonding catalysis of alkyl‐onium salts, which is promoted via the activation of electrophiles, has recently become a relevant topic in the field of onium salt chemistry. This Minireview introduces new possibilities and future directions for alkyl‐onium salt chemistry based on its use in hydrogen‐bonding catalysis and on its overall utility.     

Mussel‐Inspired Two‐Dimensional Freestanding Alkyl‐Polydopamine Janus Nanosheets

Mussel‐inspired two‐dimensional freestanding, alkyl‐polydopamine (alkyl‐PDA) Janus nanosheets, with a well‐controlled nanometer thickness and a lateral size of up to micrometers, have been developed. A self‐assembled octadecylamine (ODA) bilayer is used as the reactive template for the dopamine polymerization, resulting in the formation of well‐defined nanosheets. The alkyl‐PDA nanosheets show an amphiphilic nature with hydrophilic PDA and hydrophobic alkyl chains on opposing sides. The nanosheets can be used to functionalize many substrates and is dependent on the configuration of surface of the nanosheets. The nanosheets are quite stable, as the morphology is preserved after carbonization at 900 °C. Post‐modification of the nanosheets can be easily achieved because of the reactive nature of PDA. This work will provide a new strategic approach for fabricating polymeric Janus nanosheets, which can find applications for surface modifications, catalyst supports, and guided self‐assembly.     

Liquid‐Phase RNA Synthesis by Using Alkyl‐Chain‐Soluble Support

Recent progress in the RNA therapeutics has increased demand for the synthesis of large quantities of oligoribonucleotides. The assembly of RNA oligomers relies mainly on solid‐phase approaches. These allow rapid product purification and the ability to drive a target reaction to completion through the use of excess reagents. Despite the known advantages of solid‐phase synthesis, some issues in the process remain to be addressed, such as low and limited scale, reagent accessibility, and the use of a very large excess of reagents. Herein, we report a highly efficient and practical method of liquid‐phase synthesis of RNA oligomers by using alkyl‐chain‐soluble support. We demonstrate the utility of the liquid‐phase method through 21‐mer RNA synthesis on a gram scale.     

Selective Oxidation of Alkyl‐Substituted Polyaromatics Using Ruthenium‐Ion‐Catalyzed Oxidation

Ruthenium‐ion‐catalyzed oxidation of a range of alkylated polyaromatics has been studied. 2‐Ethylnaphthalene was used as a model substrate, and oxidation can be performed in either a conventional biphasic or in a monophasic solvent system. In either case the reaction rates and product selectivity are identical. The reaction products indicate that the aromatic ring system is oxidized in preference to the alkyl chain. This analysis is possible due to the development of a quantitative NMR protocol to determine the relative amounts of aliphatic and aromatic protons. From a systematic set of substrates we show that as the length of the alkyl chain substituent on a polyaromatic increases, the proportion of products in which the chain remains attached to the aromatic system increases. Larger polyaromatic systems, based on pyrene and phenanthrene, show greater reactivity than those with fewer aromatic rings, and the alkyl chains are more stable to oxidation.     

Alkyl‐Chain‐Regulated Charge Transfer in Fluorescent Inorganic CsPbBr3 Perovskite Solar Cells

Improved charge extraction and wide spectral absorption promote power conversion efficiency of perovskite solar cells (PSCs). The state‐of‐the‐art carbon‐based CsPbBr₃ PSCs have an inferior power output capacity because of the large optical band gap of the perovskite film and the high energy barrier at perovskite/carbon interface. Herein, we use alkyl‐chain regulated quantum dots as hole‐conductors to reduce charge recombination. By precisely controlling alkyl‐chain length of ligands, a balance between the surface dipole induced charge coulomb repulsive force and quantum tunneling distance is achieved to maximize charge extraction. A fluorescent carbon electrode is used as a cathode to harvest the unabsorbed incident light and to emit fluorescent light at 516 nm for re‐absorption by the perovskite film. The optimized PSC free of encapsulation achieves a maximum power conversion efficiency up to 10.85 % with nearly unchanged photovoltaic performances under 80 %RH, 80 °C, or light irradiation in air.