Oriented Internal Electrostatic Fields Cooperatively Promote Ground- and Excited-State Reactivity: A Case Study in Photochemical CO2 Capture
Oriented Internal Electrostatic Fields Cooperatively Promote Ground- and Excited-State Reactivity: A Case Study in Photochemical CO2 Capture
复制标题
DOI：
10.1021/jacs.9b12186
复制
发表时间：
2020-01-08
影响因子：
15
通讯作者：
Coote, Michelle L.
中科院分区：
文献类型：
--
作者：
Blyth, Mitchell T.;Noble, Benjamin B.;Coote, Michelle L.
定向静电场对化学反应的动力学和热力学都有催化作用；然而，到目前为止，绝大多数的研究都集中在基态化学上，很少考虑超过一类的反应。在本研究中，我们首先使用密度泛函理论（DFT）计算来阐明由Murakami等人最初提出的o-烷基苯基酮光化学羧化储存二氧化碳的机制。化学。Soc. 2015, 137, 14063)；然后，我们证明了由远程带电官能团（CFGs）产生的定向内部静电场可以选择性地和合作地促进基态和激发态化学反应性，沿着修正机制的所有点，以一种难以通过经典取代基效应获得的方式。特别引人注目的是，在极性越来越强的溶剂中，静电场对关键光化学转变的影响可以预见地增强，从而克服了静电催化范式的一个中心限制。我们解释这些观测，这应该很容易扩展到基态。
Oriented electrostatic fields can exert catalytic effects upon both the kinetics and the thermodynamics of chemical reactions; however, the vast majority of studies thus far have focused upon ground-state chemistry and rarely consider any more than a single class of reaction. In the present study, we first use density functional theory (DFT) calculations to clarify the mechanism of CO2 storage via photochemical carboxylation of o-alkylphenyl ketones, originally proposed by Murakami et al. (J. Am. Chem. Soc. 2015, 137, 14063); we then demonstrate that oriented internal electrostatic fields arising from remote charged functional groups (CFGs) can selectively and cooperatively promote both ground- and excited-state chemical reactivity at all points along the revised mechanism, in a manner otherwise difficult to access via classical substituent effects. What is particularly striking is that electrostatic field effects upon key photochemical transitions are predictably enhanced in increasingly polar solvents, thus overcoming a central limitation of the electrostatic catalysis paradigm. We explain these observations, which should be readily extendable to the ground state.