Abstract:H‐bonds can exert a substantial impact on the course of organic electrode reactions due to their ability to stabilize charged intermediates and products formed during these reactions, as well as facilitate proton‐coupled electron transfer (PCET) reactions. This has fundamental implications for the mechanism of organic electrode reactions, but also practical impact in supramolecular chemistry and potentially synthetic electrochemistry. My group's main focus has been on the supramolecular applications, using ele… Show more
“…The unoccupied orbital makes the boron atom in DtBuCzB act as a good electron acceptor in conjugation. Herein, p- benzoquinone ( p- BQ) was chosen as an electrochemically regulated electron donor due to its remarkable change of electric charge density before and after electroreduction and excellent electrochemical redox performance 71 – 73 . Fig.…”
Boron-doped polycyclic aromatic hydrocarbons exhibit excellent optical properties, and regulating their photophysical processes is a powerful strategy to understand the luminescence mechanism and develop new materials and applications. Herein, an electrochemically responsive B–O dynamic coordination bond is proposed, and used to regulate the photophysical processes of boron-nitrogen-doped polyaromatic hydrocarbons. The formation of the B–O coordination bond under a suitable voltage is confirmed by experiments and theoretical calculations, and B–O coordination bond can be broken back to the initial state under opposite voltage. The whole process is accompanied by reversible changes in photophysical properties. Further, electrofluorochromic devices are successfully prepared based on the above electrochemically responsive coordination bond. The success and harvest of this exploration are beneficial to understand the luminescence mechanism of boron-nitrogen-doped polyaromatic hydrocarbons, and provide ideas for design of dynamic covalent bonds and broaden material types and applications.
“…The unoccupied orbital makes the boron atom in DtBuCzB act as a good electron acceptor in conjugation. Herein, p- benzoquinone ( p- BQ) was chosen as an electrochemically regulated electron donor due to its remarkable change of electric charge density before and after electroreduction and excellent electrochemical redox performance 71 – 73 . Fig.…”
Boron-doped polycyclic aromatic hydrocarbons exhibit excellent optical properties, and regulating their photophysical processes is a powerful strategy to understand the luminescence mechanism and develop new materials and applications. Herein, an electrochemically responsive B–O dynamic coordination bond is proposed, and used to regulate the photophysical processes of boron-nitrogen-doped polyaromatic hydrocarbons. The formation of the B–O coordination bond under a suitable voltage is confirmed by experiments and theoretical calculations, and B–O coordination bond can be broken back to the initial state under opposite voltage. The whole process is accompanied by reversible changes in photophysical properties. Further, electrofluorochromic devices are successfully prepared based on the above electrochemically responsive coordination bond. The success and harvest of this exploration are beneficial to understand the luminescence mechanism of boron-nitrogen-doped polyaromatic hydrocarbons, and provide ideas for design of dynamic covalent bonds and broaden material types and applications.
“…By the introduction of electroactive moieties into heteroaromatic urea derivatives, complexation processes can be followed not only by NMR and UV/Vis spectroscopy, but also by electrochemical methods, e.g., by cyclic voltammetry (CV). As another feature, the strength of H-bonds can be altered by electron transfer to create redox-responsive H-bonded complexes [61,62] that can result in the development of stimuli-responsive formation of supramolecular polymers.…”
Ureido-heterocycles exhibiting different triple- and quadruple H-bonding patterns are useful building blocks in the construction of supramolecular polymers, self-healing materials, stimuli-responsive devices, catalysts and sensors. The heterocyclic group may provide hydrogen bond donor/acceptor sites to supplement those in the urea core, and they can also bind metals and can be modified by pH, redox reactions or irradiation. In the present review, the main structural features of these derivatives are discussed, including the effect of tautomerization and conformational isomerism on self-assembly and complex formation. Some examples of their use as building blocks in different molecular architectures and supramolecular polymers, with special emphasis on biomedical applications, are presented. The role of the heterocyclic functionality in catalytic and sensory applications is also outlined.
“…Therefore, researchers continue to develop and refine new methods to enable the efficient synthesis of complex structures with diverse functionalities by choosing appropriate weak or non-covalent interactions . The weak interactions such as cation−π, anion−π, hydrogen-bonding (H-bonding), halogen-bonding (XB), − hydrophobic effect, S–H···π and sulfur···oxygen, and others are widely used in chemistry to control many chemical reactions. However, the use of stereoelectronic effects for reaction control in organic synthesis has gained significant attention in recent years, providing powerful strategies for precise manipulation of reaction outcomes, selectivity, and efficiency. − The stereoelectronic effects can be referred to as “ stabilizing electronic interactions maximized by a particular geometric arrangement which can be traced to a favorable orbital overlap ”…”
The stereoselective synthesis of Z-anti-Markovnikov styryl sulfides via an anionic thiolate−alkyne addition reaction was achieved when the terminal alkynes and benzyl mercaptans were reacted using t BuOLi (0.5 equiv) in EtOH under ambient conditions. Exclusive stereoselectivity (ca. 100%) was achieved by stereoelectronic control via anti-periplanar and anti-Markovnikov addition of benzylthiolates to phenylacetylenes. Solvolysis of lithium thiolate ion pairs in ethanol significantly suppresses the competing formation of the E-isomer. A remarkable enhancement of the Z-selectivity under a longer reaction time was observed.
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