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Synthesis, spectroscopy and QM/MM simulations of a biomimetic ultrafast light-driven molecular motor

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Abstract

A molecular motor potentially performing a continuous unidirectional rotation is studied by a multidisciplinary approach including organic synthesis, transient spectroscopy and excited state trajectory calculations. A stereogenic center was introduced in the N-alkylated indanylidene–pyrroline Schiff base framework of a previously investigated light-driven molecular switch in order to achieve the unidirectional C=C rotary motion typical of Feringa’s motor. Here we report that the specific substitution pattern of the designed chiral molecule must critically determine the unidirectional efficiency of the light-induced rotary motion. More specifically, we find that a stereogenic center containing a methyl group and a hydrogen atom as substituents does not create a differential steric effect large enough to fully direct the motion in either the clockwise or counterclockwise direction especially along the E → Z coordinate. However, due to the documented ultrafast character and electronic circular dichroism activity of the investigated system, we find that it provides the basis for development of a novel generation of rotary motors with a biomimetic framework and operating on a picosecond time scale.

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Author information

Author notes

  1. Igor Schapiro

    Present address: Fritz Haber Center for Molecular Dynamics Research at the Institute of Chemistry, the Hebrew University of Jerusalem, 91904, Jerusalem, Israel

  2. Mark Huntress

    Present address: Patrick Henry Community College in Martinsville, 24112, VA, USA

Authors and Affiliations

  1. Université de Strasbourg, CNRS, UMR 7504, Institut de Physique et Chimie des Matériaux de Strasbourg, 23 du Loess, 67034, Strasbourg, France

    Igor Schapiro, Moussa Gueye, Gabriel Marchand, Stefan Haacke & Jérémie Léonard

  2. Dipartimento di Biotecnologia, Chimica e Farmacia (Dipartimento di Eccellenza 2018-2022), Università degli Studi di Siena, via Aldo Moro 2, I-53100, Siena, Italy

    Marco Paolino, Stefania Fusi & Massimo Olivucci

  3. Area de Química Física, Universidad de Extremadura, Avenida de Elvas sn, E-06071, Badajoz, Spain

    M. Elena Martin

  4. Chemistry Department, Bowling Green State University, 43403, Bowling Green, Ohio , USA

    Mark Huntress & Massimo Olivucci

  5. Division of Theoretical Chemistry, Kemicentrum, Lund University, P.O. Box 124, SE-221 00, Lund, Sweden

    Victor P. Vysotskiy & Valera Veryazov

Authors
  1. Igor Schapiro
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  2. Moussa Gueye
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  3. Marco Paolino
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  4. Stefania Fusi
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  5. Gabriel Marchand
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  6. Stefan Haacke
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  7. M. Elena Martin
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  9. Victor P. Vysotskiy
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  10. Valera Veryazov
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  11. Jérémie Léonard
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  12. Massimo Olivucci
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Corresponding author

Correspondence to Massimo Olivucci.

Additional information

Dedicated to the memory of Professor Ugo Mazzucato of the University of Perugia, Italy.

Electronic supplementary information (ESI) available: Two trajectory movies (echiral.006.md.xyz and zchiral.004.md.xyz). See DOI: 10.1039/c9pp00223e

These authors have equally contributed to the research.

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Schapiro, I., Gueye, M., Paolino, M. et al. Synthesis, spectroscopy and QM/MM simulations of a biomimetic ultrafast light-driven molecular motor. Photochem Photobiol Sci 18, 2259–2269 (2019). https://doi.org/10.1039/c9pp00223e

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  • DOI: https://doi.org/10.1039/c9pp00223e

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