Department of Chemistry and Biochemistry, San Diego State University, 5500 Campanile Dr, San Diego, CA, 92182, USA.
Chem Rec. 2021 Sep;21(9):2488-2501. doi: 10.1002/tcr.202100186. Epub 2021 Sep 6.
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 electron transfer to alter the strength of H-bonds to create highly redox-responsive H-bond dimers. Initially we sought to avoid proton transfer because we feared that would lead to irreversible electrochemistry. However, inevitably proton transfer did show up, but, to our surprise, did not lead to irreversible electrochemistry. To explain this, we developed a new mechanism, the "wedge scheme", that shows how H-bonding can facilitate reversible electron and proton transfer. This insight recently led us to a new PCET-based design strategy for the creation of our most highly redox-responsive H-bond dimers yet.
氢键由于能够稳定有机电极反应过程中形成的带电中间体和产物，并促进质子耦合电子转移（PCET）反应，因此对有机电极反应的机制具有重要意义，但也对超分子化学和潜在的合成电化学具有实际影响。我的研究小组主要关注的是超分子应用，利用电子转移来改变氢键的强度，从而创建高度氧化还原响应的氢键二聚体。最初，我们试图避免质子转移，因为我们担心这会导致不可逆的电化学。然而，质子转移不可避免地出现了，但令我们惊讶的是，它并没有导致不可逆的电化学。为了解释这一点，我们开发了一种新的机制，即“楔入方案”，该方案展示了氢键如何促进可逆的电子和质子转移。这一见解最近使我们能够基于 PCET 设计一种新的策略，用于创造我们迄今为止最具氧化还原响应性的氢键二聚体。
