Enhanced Diastereocontrol via Strong Light–Matter Interactions in an Optical Cavity
Enhanced Diastereocontrol via Strong Light–Matter Interactions in an Optical Cavity
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通过光腔中的强光与物质相互作用增强非对映控制
DOI：
10.1021/acs.jpca.2c07134
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
DePrince, A. Eugene
中科院分区：
文献类型：
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作者：
Vu, Nam;McLeod, Grace M.;Hanson, Kenneth;DePrince, A. Eugene
手性分子外消旋混合物的对映纯化对一系列应用具有重要意义。最近的研究表明，手性基团定向光异构化是一种很有前途的方法，以获得对映丰富的BINOL外消旋混合物，但增加对非对映异构体过量（de）的控制是其广泛应用所必需的。在这里，我们发展了一个腔量子电动力学（QED）的时间依赖密度泛函理论的推广，并通过计算证明了强光-物质耦合可以改变BINOL的手性基团定向光异构化。腔模偏振和腔内分子的相对取向决定了腔相互作用的性质，这种相互作用要么增强(R)-BINOL非对映体的优势（从17%增加到≈40%），要么使(S)-BINOL导数的优势逆转（≈34%de）。后一个结果是特别显著的，因为它表明对非对映体的偏好可以通过取向控制来影响，而不改变指向基团的手性。我们证明了所观察到的效应是由腔诱导的基态Kohn-Sham轨道的变化引起的。
The enantiopurification of racemic mixtures of chiral molecules is important for a range of applications. Recent work has shown that chiral group-directed photoisomerization is a promising approach to enantioenrich racemic mixtures of BINOL, but increased control of the diasteriomeric excess (de) is necessary for its broad utility. Here we develop a cavity quantum electrodynamics (QED) generalization of time-dependent density functional theory and demonstrate computationally that strong light–matter coupling can alter thedeof the chiral group-directed photoisomerization of BINOL. The relative orientation of the cavity mode polarization and the molecules in the cavity dictates the nature of the cavity interactions, which either enhance thedeof the (R)-BINOL diasteriomer (from 17% to ≈40%) or invert the favorability to the (S)-BINOL derivative (to ≈34%de). The latter outcome is particularly remarkable because it indicates that the preference in diasteriomer can be influenced via orientational control, without changing the chirality of the directing group. We demonstrate that the observed effect stems from cavity-induced changes to the Kohn–Sham orbitals of the ground state.