In contrast to the notion that enantiospecific chemical reactions require a chiral reagent molecule or catalyst, this work shows that enantioselective chemical transformations can be induced by the electron spin itself. As electrons are injected from a magnetized electrode into an adsorbed molecule, they have a distinct spin orientation relative to their velocity; i.e., they have a well-defined helicity. Thus, it is possible to replace a conventional enantiopure chemical reagent by spin-polarized electrons that provide the chiral bias for enantioselective reactions. Three examples of enantioselective chemistry, resulting from electron spin polarization, are presented. The first example demonstrates enantioselective association of a chiral molecule with an achiral self-assembled monolayer film that is spin-polarized. The other two studies show that the chiral bias provided by the electron helicity can drive both reduction and oxidation enantiospecific electrochemical reactions. In each case, the enantioselectivity does not result from enantiospecific interaction of the molecule with the ferromagnetic electrode, but rather it arises from the polarized spin that crosses the interface between the substrate and the molecule. In all three cases, the direction of the electron spin polarization defines the sense (left-handed versus right-handed) of the enantioselectivity. This work demonstrates a new mechanism for realizing enantioselective chemistry.

The electron spin as a chiral reagent / Naaman, Ron; Metzger, Tzuriel S; Mishra, Suryakant; Bloom, Brian P; Goren, Naama; Neubauer, Avner; Shmul, Guy; Wei, Jimeng; Yochelis, Shira; Tassinari, Francesco; Fontanesi, Claudio; Waldeck, David H; Paltiel, Yossi. - In: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION. - ISSN 1433-7851. - 59:4(2020), pp. 1653-1658. [10.1002/anie.201911400]

The electron spin as a chiral reagent

Tassinari, Francesco;Fontanesi, Claudio;
2020

Abstract

In contrast to the notion that enantiospecific chemical reactions require a chiral reagent molecule or catalyst, this work shows that enantioselective chemical transformations can be induced by the electron spin itself. As electrons are injected from a magnetized electrode into an adsorbed molecule, they have a distinct spin orientation relative to their velocity; i.e., they have a well-defined helicity. Thus, it is possible to replace a conventional enantiopure chemical reagent by spin-polarized electrons that provide the chiral bias for enantioselective reactions. Three examples of enantioselective chemistry, resulting from electron spin polarization, are presented. The first example demonstrates enantioselective association of a chiral molecule with an achiral self-assembled monolayer film that is spin-polarized. The other two studies show that the chiral bias provided by the electron helicity can drive both reduction and oxidation enantiospecific electrochemical reactions. In each case, the enantioselectivity does not result from enantiospecific interaction of the molecule with the ferromagnetic electrode, but rather it arises from the polarized spin that crosses the interface between the substrate and the molecule. In all three cases, the direction of the electron spin polarization defines the sense (left-handed versus right-handed) of the enantioselectivity. This work demonstrates a new mechanism for realizing enantioselective chemistry.
2020
17-ott-2019
59
4
1653
1658
The electron spin as a chiral reagent / Naaman, Ron; Metzger, Tzuriel S; Mishra, Suryakant; Bloom, Brian P; Goren, Naama; Neubauer, Avner; Shmul, Guy; Wei, Jimeng; Yochelis, Shira; Tassinari, Francesco; Fontanesi, Claudio; Waldeck, David H; Paltiel, Yossi. - In: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION. - ISSN 1433-7851. - 59:4(2020), pp. 1653-1658. [10.1002/anie.201911400]
Naaman, Ron; Metzger, Tzuriel S; Mishra, Suryakant; Bloom, Brian P; Goren, Naama; Neubauer, Avner; Shmul, Guy; Wei, Jimeng; Yochelis, Shira; Tassinari, Francesco; Fontanesi, Claudio; Waldeck, David H; Paltiel, Yossi
File in questo prodotto:
File Dimensione Formato  
Angewandte_Anie.201911400.pdf

Accesso riservato

Tipologia: Versione pubblicata dall'editore
Dimensione 2.02 MB
Formato Adobe PDF
2.02 MB Adobe PDF   Visualizza/Apri   Richiedi una copia
POST PRINT_the electron.pdf

Open access

Tipologia: Versione dell'autore revisionata e accettata per la pubblicazione
Dimensione 1.25 MB
Formato Adobe PDF
1.25 MB Adobe PDF Visualizza/Apri
Pubblicazioni consigliate

Licenza Creative Commons
I metadati presenti in IRIS UNIMORE sono rilasciati con licenza Creative Commons CC0 1.0 Universal, mentre i file delle pubblicazioni sono rilasciati con licenza Attribuzione 4.0 Internazionale (CC BY 4.0), salvo diversa indicazione.
In caso di violazione di copyright, contattare Supporto Iris

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/1186584
Citazioni
  • ???jsp.display-item.citation.pmc??? 21
  • Scopus 65
  • ???jsp.display-item.citation.isi??? 63
social impact