All-photochemical rotation of molecular motors with a phosphorus stereoelement

Gregory B. Boursalian; Eise R. Nijboer; Ruth Dorel; Lukas Pfeifer; Omer Markovitch; Alex Blokhuis; Ben L. Feringa

doi:10.1021/jacs.0c08249

All-photochemical rotation of molecular motors with a phosphorus stereoelement

Gregory B. Boursalian, Eise R. Nijboer, Ruth Dorel, Lukas Pfeifer, Omer Markovitch, Alex Blokhuis, Ben L. Feringa^*

^*Corresponding author voor dit werk

Onderzoeksoutput › Academic › peer review

32 Citaten (Scopus)

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Unidirectional molecular rotation based on alternating photochemical and thermal isomerizations of overcrowded alkenes is well established, but rotary cycles based purely on photochemical isomerizations are rare. Herein we report three new second-generation molecular motors featuring a phosphorus center in the lower half, which engenders a unique element of axial chirality. These motors exhibit unusual behavior, in that all four diastereomeric states can interconvert solely photochemically. Kinetic analysis and modeling reveal that the behavior of the new motors is consistent with all-photochemical unidirectional rotation. Furthermore, X-ray crystal structures of all four diastereomeric states of two of these new motors were obtained, which constitute the first achievements of crystallographic characterization of the full 360° rotational cycle of overcrowded-alkene-based molecular motors. Finally, the axial phosphorus stereoelement in the phosphine motor can be thermally inverted, and this epimerization enables a “shortcut” of the traditional rotational cycle of these compounds.

Originele taal-2	English
Pagina's (van-tot)	16868-16876
Aantal pagina's	9
Tijdschrift	Journal of the American Chemical Society
Volume	142
Nummer van het tijdschrift	39
DOI's	https://doi.org/10.1021/jacs.0c08249
Status	Published - 30-sep.-2020

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10.1021/jacs.0c08249Licentie: CC BY-NC-ND

All-Photochemical Rotation of Molecular Motors with a Phosphorus StereoelementFinal publisher's version, 3,15 MBLicentie: CC BY-NC-ND

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CCDC 2019763: Experimental Crystal Structure Determination
Boursalian, G. (Contributor), Nijboer, E. R. (Contributor), Dorel Bruscas, R. (Contributor), Pfeifer, L. (Contributor), Markovitch, O. (Contributor), Blokhuis, A. (Contributor) & Feringa, B. L. (Contributor), University of Groningen, 28-jul.-2020
DOI: 10.5517/ccdc.csd.cc25sqnc
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oLife Fellowship Programme
Roos, W. (Hoofdonderzoeker), van der Tak, F. (Hoofdonderzoeker), Zijlstra, W. (Hoofdonderzoeker), Dobos, V. (Postdoc), Heinen, L. (Postdoc), Thangaratnarajah, C. (Postdoc), Hoekzema, M. (Postdoc), Blokhuis, A. (Postdoc), Mascotti, L. (Postdoc), Padin Santos, D. (Postdoc), Chopra, A. (Postdoc), Obermaier, S. (Postdoc), Driver, M. (Postdoc), Moreira Goulart, M. (Postdoc), Sasidharan, S. (Postdoc), Samar Mahapatra, S. (Postdoc), Zylstra, A. (Postdoc), Geiger, Y. (Postdoc), Llopis Lorente, A. (Postdoc), Aschmann, D. (Postdoc) & Kulala Vittala, S. (Postdoc)
01/04/2019 → 31/03/2024
Project: Research

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@article{0f69b1bf02864b55bf6347e942bfff51,

title = "All-photochemical rotation of molecular motors with a phosphorus stereoelement",

abstract = "Unidirectional molecular rotation based on alternating photochemical and thermal isomerizations of overcrowded alkenes is well established, but rotary cycles based purely on photochemical isomerizations are rare. Herein we report three new second-generation molecular motors featuring a phosphorus center in the lower half, which engenders a unique element of axial chirality. These motors exhibit unusual behavior, in that all four diastereomeric states can interconvert solely photochemically. Kinetic analysis and modeling reveal that the behavior of the new motors is consistent with all-photochemical unidirectional rotation. Furthermore, X-ray crystal structures of all four diastereomeric states of two of these new motors were obtained, which constitute the first achievements of crystallographic characterization of the full 360° rotational cycle of overcrowded-alkene-based molecular motors. Finally, the axial phosphorus stereoelement in the phosphine motor can be thermally inverted, and this epimerization enables a “shortcut” of the traditional rotational cycle of these compounds.",

keywords = "PYRAMIDAL INVERSION, PHOTORESOLUTION, PHOTOTRIGGERS",

author = "Boursalian, {Gregory B.} and Nijboer, {Eise R.} and Ruth Dorel and Lukas Pfeifer and Omer Markovitch and Alex Blokhuis and Feringa, {Ben L.}",

note = "Funding Information: This work was supported financially by The Netherlands Organization for Scientific Research (NWO-CW), the European Research Council (ERC, advanced grant no. 694345 to B.L.F.), the European Commission (MSC-IV No. 793082 to L.P.), the Ramon Areces Foundation (Postdoctoral fellowship to R.D.), NWA StartImpuls (fellowship for O.M.), and the Ministry of Education, Culture and Science (Gravitation Program no. 024.001.035). The authors are grateful to Pieter van der Meulen and Dr. Johan Kemmink (University of Groningen) for assistance with NMR measurements. Renze Sneep (University of Groningen) is also acknowledged for mass spectral analysis. We thank the Center for Information Technology of the University of Groningen for providing access to the Peregrine high performance computing cluster. Funding Information: This work was supported financially by The Netherlands Organization for Scientific Research (NWO-CW), the European Research Council (ERC, advanced grant no. 694345 to B.L.F.), the European Commission (MSC-IV No. 793082 to L.P.), the Ram{\'o}n Areces Foundation (Postdoctoral fellowship to R.D.), NWA StartImpuls (fellowship for O.M.), and the Ministry of Education, Culture and Science (Gravitation Program no. 024.001.035). Publisher Copyright: {\textcopyright} 2020 American Chemical Society Copyright: Copyright 2021 Elsevier B.V., All rights reserved.",

year = "2020",

month = sep,

day = "30",

doi = "10.1021/jacs.0c08249",

language = "English",

volume = "142",

pages = "16868--16876",

journal = "Journal of the American Chemical Society",

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publisher = "AMER CHEMICAL SOC",

number = "39",

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TY - JOUR

T1 - All-photochemical rotation of molecular motors with a phosphorus stereoelement

AU - Boursalian, Gregory B.

AU - Nijboer, Eise R.

AU - Dorel, Ruth

AU - Pfeifer, Lukas

AU - Markovitch, Omer

AU - Blokhuis, Alex

AU - Feringa, Ben L.

N1 - Funding Information: This work was supported financially by The Netherlands Organization for Scientific Research (NWO-CW), the European Research Council (ERC, advanced grant no. 694345 to B.L.F.), the European Commission (MSC-IV No. 793082 to L.P.), the Ramon Areces Foundation (Postdoctoral fellowship to R.D.), NWA StartImpuls (fellowship for O.M.), and the Ministry of Education, Culture and Science (Gravitation Program no. 024.001.035). The authors are grateful to Pieter van der Meulen and Dr. Johan Kemmink (University of Groningen) for assistance with NMR measurements. Renze Sneep (University of Groningen) is also acknowledged for mass spectral analysis. We thank the Center for Information Technology of the University of Groningen for providing access to the Peregrine high performance computing cluster. Funding Information: This work was supported financially by The Netherlands Organization for Scientific Research (NWO-CW), the European Research Council (ERC, advanced grant no. 694345 to B.L.F.), the European Commission (MSC-IV No. 793082 to L.P.), the Ramón Areces Foundation (Postdoctoral fellowship to R.D.), NWA StartImpuls (fellowship for O.M.), and the Ministry of Education, Culture and Science (Gravitation Program no. 024.001.035). Publisher Copyright: © 2020 American Chemical Society Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2020/9/30

Y1 - 2020/9/30

N2 - Unidirectional molecular rotation based on alternating photochemical and thermal isomerizations of overcrowded alkenes is well established, but rotary cycles based purely on photochemical isomerizations are rare. Herein we report three new second-generation molecular motors featuring a phosphorus center in the lower half, which engenders a unique element of axial chirality. These motors exhibit unusual behavior, in that all four diastereomeric states can interconvert solely photochemically. Kinetic analysis and modeling reveal that the behavior of the new motors is consistent with all-photochemical unidirectional rotation. Furthermore, X-ray crystal structures of all four diastereomeric states of two of these new motors were obtained, which constitute the first achievements of crystallographic characterization of the full 360° rotational cycle of overcrowded-alkene-based molecular motors. Finally, the axial phosphorus stereoelement in the phosphine motor can be thermally inverted, and this epimerization enables a “shortcut” of the traditional rotational cycle of these compounds.

AB - Unidirectional molecular rotation based on alternating photochemical and thermal isomerizations of overcrowded alkenes is well established, but rotary cycles based purely on photochemical isomerizations are rare. Herein we report three new second-generation molecular motors featuring a phosphorus center in the lower half, which engenders a unique element of axial chirality. These motors exhibit unusual behavior, in that all four diastereomeric states can interconvert solely photochemically. Kinetic analysis and modeling reveal that the behavior of the new motors is consistent with all-photochemical unidirectional rotation. Furthermore, X-ray crystal structures of all four diastereomeric states of two of these new motors were obtained, which constitute the first achievements of crystallographic characterization of the full 360° rotational cycle of overcrowded-alkene-based molecular motors. Finally, the axial phosphorus stereoelement in the phosphine motor can be thermally inverted, and this epimerization enables a “shortcut” of the traditional rotational cycle of these compounds.

KW - PYRAMIDAL INVERSION

KW - PHOTORESOLUTION

KW - PHOTOTRIGGERS

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U2 - 10.1021/jacs.0c08249

DO - 10.1021/jacs.0c08249

M3 - Article

C2 - 32905701

AN - SCOPUS:85092439336

SN - 0002-7863

VL - 142

SP - 16868

EP - 16876

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 39

ER -

All-photochemical rotation of molecular motors with a phosphorus stereoelement

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