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由电子自旋极化诱导的不对称反应。

Asymmetric reactions induced by electron spin polarization.

作者信息

Bloom B P, Lu Y, Metzger Tzuriel, Yochelis Shira, Paltiel Yossi, Fontanesi Claudio, Mishra Suryakant, Tassinari Francesco, Naaman Ron, Waldeck D H

机构信息

Chemistry Department, University of Pittsburgh, Pittsburgh, PA 15260, USA.

Applied Physics Department and the Center for Nano-Science and Nano-Technology, The Hebrew University of Jerusalem, Jerusalem, 91904, Israel.

出版信息

Phys Chem Chem Phys. 2020 Oct 7;22(38):21570-21582. doi: 10.1039/d0cp03129a.

DOI:10.1039/d0cp03129a
PMID:32697241
Abstract

Essential aspects of the chiral induced spin selectivity (CISS) effect and their implications for spin-controlled chemistry and asymmetric electrochemical reactions are described. The generation of oxygen through electrolysis is discussed as an example in which chirality-based spin-filtering and spin selection rules can be used to improve the reaction's efficiency and selectivity. Next the discussion shifts to illustrate how the spin selectivity of chiral molecules (CISS properties) allows one to use the electron spin as a chiral bias for inducing asymmetric reactions and promoting enantiospecific processes. Two enantioselective electrochemical reactions that have used polarized electron spins as a chiral reagent are described; enantioselective electroreduction to resolve an enantiomer from a racemic mixture and an oxidative electropolymerization to generate a chiral polymer from achiral monomers. A complementary approach that has used spin-polarized, but otherwise achiral, molecular films to enantiospecifically associate with one enantiomer from a racemic mixture is also discussed. Each of these reaction types use magnetized films to generate the spin polarized electrons and the enantiospecificity can be selected by choice of the magnetization direction, North pole versus South pole. Possible paths for future research in this area and its compatibility with existing methods based on chiral electrodes are discussed.

摘要

描述了手性诱导自旋选择性(CISS)效应的基本方面及其对自旋控制化学和不对称电化学反应的影响。以电解产氧为例进行了讨论,在该例子中,基于手性的自旋过滤和自旋选择规则可用于提高反应的效率和选择性。接下来,讨论转向说明手性分子的自旋选择性(CISS特性)如何使人们能够将电子自旋用作手性偏压,以诱导不对称反应并促进对映体特异性过程。描述了两个使用极化电子自旋作为手性试剂的对映选择性电化学反应;用于从外消旋混合物中拆分对映体的对映选择性电还原反应,以及用于从非手性单体生成手性聚合物的氧化电聚合反应。还讨论了一种互补方法,该方法使用自旋极化但其他方面为非手性的分子膜与外消旋混合物中的一种对映体进行对映体特异性缔合。这些反应类型中的每一种都使用磁化膜来产生自旋极化电子,并且可以通过选择磁化方向(北极与南极)来选择对映体特异性。讨论了该领域未来研究的可能途径及其与基于手性电极的现有方法的兼容性。

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