A visible-light-driven molecular motor based on barbituric acid

Kim Kuntze; Daisy R.S. Pooler; Mariangela Di Donato; Michiel F. Hilbers; Pieter van der Meulen; Wybren Jan Buma; Arri Priimagi; Ben L. Feringa; Stefano Crespi

doi:10.1039/d3sc03090c

A visible-light-driven molecular motor based on barbituric acid

Kim Kuntze, Daisy R.S. Pooler, Mariangela Di Donato, Michiel F. Hilbers, Pieter van der Meulen, Wybren Jan Buma, Arri Priimagi, Ben L. Feringa, Stefano Crespi

Materials Science and Environmental Engineering

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Abstract

We present a class of visible-light-driven molecular motors based on barbituric acid. Due to a serendipitous reactivity we observed during their synthesis, these motors possess a tertiary stereogenic centre on the upper half, characterised by a hydroxy group. Using a combination of femto- and nanosecond transient absorption spectroscopy, molecular dynamics simulations and low-temperature ¹H NMR experiments we found that these motors operate similarly to push-pull second-generation overcrowded alkene-based molecular motors. Interestingly, the hydroxy group at the stereocentre enables a hydrogen bond with the carbonyl groups of the barbituric acid lower half, which drives a sub-picosecond excited-state isomerisation, as observed spectroscopically. Computational simulations predict an excited state “lasso” mechanism where the intramolecular hydrogen bond pulls the molecule towards the formation of the metastable state, with a high predicted quantum yield of isomerisation (68%) in gas phase.

Original language	English
Pages (from-to)	8458-8465
Journal	Chemical Science
Volume	14
Issue number	32
DOIs	https://doi.org/10.1039/d3sc03090c
Publication status	Published - 28 Aug 2023
Publication type	A1 Journal article-refereed

Funding

K. K. and D. R. S. P. thank Pieter van der Meulen and Dr Johan Kemmink for guidance with low temperature NMR measurements, Renze Sneep for guidance with preparative SFC, and Jacob Baas for guidance in measuring XRD. D. R. S. P. and M. D. D. thank Laura Bussotti, Sandra Doria and Alessandro Iagatti for supporting the femtosecond transient absorption spectroscopy measurements. We thank the Centre for Information Technology of the University of Groningen for their support and for providing access to the Peregrine high performance computing cluster. Financial support from the Horizon 2020 Framework Programme (ERC Advanced Investigator Grant No. 694345 to B. L. F., ERC Consolidator Grant No. 101045223 for A. P.), the Netherlands Ministry of Education, Culture and Science (Gravitation Programme 024.001.035 to B. L. F.), the Marie Skłodowska-Curie Action (Individual Fellowship No. 838280 to S. C.) and the Swedish Vetenskapsrådet (for the Starting Grant 2021-05414 to S. C.). The Tampere University Graduate School (K. K.), Finnish Cultural Foundation (K. K.), and Tampere Science Fund (K. K.) are gratefully acknowledged. This project has received funding from the European Union's Horizon 2020 Research and Innovation Programme (Laserlab-Europe No. 871124 to M. D. D. and D. R. S. P.) and Academy of Finland Center of Excellence “Life-Inspired Hybrid Materials Research” (LIBER, No. 346107). We thank the Swedish National Infrastructure for Computations (SNIC) for a Small Compute Grant (SNIC 2022/22-525).

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Publication forum level 3

ASJC Scopus subject areas

General Chemistry

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10.1039/d3sc03090cLicence: CC BY

A visible-light-driven molecular motorFinal published version, 1.93 MBLicence: CC BY

https://urn.fi/URN:NBN:fi:tuni-202309128122Licence: CC BY

CCDC 2269893: Experimental Crystal Structure Determination
Kuntze, K. (Creator), Pooler, D. R. S. (Contributor), Di Donato, M. (Contributor), Hilbers, M. F. (Contributor), van der Meulen, P. (Contributor), Buma, W. J. (Contributor), Priimagi, A. (Contributor), Feringa, B. L. (Contributor) & Crespi, S. (Contributor), Cambridge Crystallographic Data Centre, 14 Jun 2023
DOI: 10.5517/ccdc.csd.cc2g60c2
Dataset

Cite this

@article{bdd4586bde604326baa885938beaf576,

title = "A visible-light-driven molecular motor based on barbituric acid",

abstract = "We present a class of visible-light-driven molecular motors based on barbituric acid. Due to a serendipitous reactivity we observed during their synthesis, these motors possess a tertiary stereogenic centre on the upper half, characterised by a hydroxy group. Using a combination of femto- and nanosecond transient absorption spectroscopy, molecular dynamics simulations and low-temperature 1H NMR experiments we found that these motors operate similarly to push-pull second-generation overcrowded alkene-based molecular motors. Interestingly, the hydroxy group at the stereocentre enables a hydrogen bond with the carbonyl groups of the barbituric acid lower half, which drives a sub-picosecond excited-state isomerisation, as observed spectroscopically. Computational simulations predict an excited state “lasso” mechanism where the intramolecular hydrogen bond pulls the molecule towards the formation of the metastable state, with a high predicted quantum yield of isomerisation (68%) in gas phase.",

author = "Kim Kuntze and Pooler, {Daisy R.S.} and {Di Donato}, Mariangela and Hilbers, {Michiel F.} and {van der Meulen}, Pieter and Buma, {Wybren Jan} and Arri Priimagi and Feringa, {Ben L.} and Stefano Crespi",

note = "Funding Information: K. K. and D. R. S. P. thank Pieter van der Meulen and Dr Johan Kemmink for guidance with low temperature NMR measurements, Renze Sneep for guidance with preparative SFC, and Jacob Baas for guidance in measuring XRD. D. R. S. P. and M. D. D. thank Laura Bussotti, Sandra Doria and Alessandro Iagatti for supporting the femtosecond transient absorption spectroscopy measurements. We thank the Centre for Information Technology of the University of Groningen for their support and for providing access to the Peregrine high performance computing cluster. Financial support from the Horizon 2020 Framework Programme (ERC Advanced Investigator Grant No. 694345 to B. L. F., ERC Consolidator Grant No. 101045223 for A. P.), the Netherlands Ministry of Education, Culture and Science (Gravitation Programme 024.001.035 to B. L. F.), the Marie Sk{\l}odowska-Curie Action (Individual Fellowship No. 838280 to S. C.) and the Swedish Vetenskapsr{\aa}det (for the Starting Grant 2021-05414 to S. C.). The Tampere University Graduate School (K. K.), Finnish Cultural Foundation (K. K.), and Tampere Science Fund (K. K.) are gratefully acknowledged. This project has received funding from the European Union's Horizon 2020 Research and Innovation Programme (Laserlab-Europe No. 871124 to M. D. D. and D. R. S. P.) and Academy of Finland Center of Excellence “Life-Inspired Hybrid Materials Research” (LIBER, No. 346107). We thank the Swedish National Infrastructure for Computations (SNIC) for a Small Compute Grant (SNIC 2022/22-525). Publisher Copyright: {\textcopyright} 2023 The Royal Society of Chemistry",

year = "2023",

month = aug,

day = "28",

doi = "10.1039/d3sc03090c",

language = "English",

volume = "14",

pages = "8458--8465",

journal = "Chemical Science",

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publisher = "Royal Society of Chemistry",

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T1 - A visible-light-driven molecular motor based on barbituric acid

AU - Kuntze, Kim

AU - Pooler, Daisy R.S.

AU - Di Donato, Mariangela

AU - Hilbers, Michiel F.

AU - van der Meulen, Pieter

AU - Buma, Wybren Jan

AU - Priimagi, Arri

AU - Feringa, Ben L.

AU - Crespi, Stefano

N1 - Funding Information: K. K. and D. R. S. P. thank Pieter van der Meulen and Dr Johan Kemmink for guidance with low temperature NMR measurements, Renze Sneep for guidance with preparative SFC, and Jacob Baas for guidance in measuring XRD. D. R. S. P. and M. D. D. thank Laura Bussotti, Sandra Doria and Alessandro Iagatti for supporting the femtosecond transient absorption spectroscopy measurements. We thank the Centre for Information Technology of the University of Groningen for their support and for providing access to the Peregrine high performance computing cluster. Financial support from the Horizon 2020 Framework Programme (ERC Advanced Investigator Grant No. 694345 to B. L. F., ERC Consolidator Grant No. 101045223 for A. P.), the Netherlands Ministry of Education, Culture and Science (Gravitation Programme 024.001.035 to B. L. F.), the Marie Skłodowska-Curie Action (Individual Fellowship No. 838280 to S. C.) and the Swedish Vetenskapsrådet (for the Starting Grant 2021-05414 to S. C.). The Tampere University Graduate School (K. K.), Finnish Cultural Foundation (K. K.), and Tampere Science Fund (K. K.) are gratefully acknowledged. This project has received funding from the European Union's Horizon 2020 Research and Innovation Programme (Laserlab-Europe No. 871124 to M. D. D. and D. R. S. P.) and Academy of Finland Center of Excellence “Life-Inspired Hybrid Materials Research” (LIBER, No. 346107). We thank the Swedish National Infrastructure for Computations (SNIC) for a Small Compute Grant (SNIC 2022/22-525). Publisher Copyright: © 2023 The Royal Society of Chemistry

PY - 2023/8/28

Y1 - 2023/8/28

N2 - We present a class of visible-light-driven molecular motors based on barbituric acid. Due to a serendipitous reactivity we observed during their synthesis, these motors possess a tertiary stereogenic centre on the upper half, characterised by a hydroxy group. Using a combination of femto- and nanosecond transient absorption spectroscopy, molecular dynamics simulations and low-temperature 1H NMR experiments we found that these motors operate similarly to push-pull second-generation overcrowded alkene-based molecular motors. Interestingly, the hydroxy group at the stereocentre enables a hydrogen bond with the carbonyl groups of the barbituric acid lower half, which drives a sub-picosecond excited-state isomerisation, as observed spectroscopically. Computational simulations predict an excited state “lasso” mechanism where the intramolecular hydrogen bond pulls the molecule towards the formation of the metastable state, with a high predicted quantum yield of isomerisation (68%) in gas phase.

AB - We present a class of visible-light-driven molecular motors based on barbituric acid. Due to a serendipitous reactivity we observed during their synthesis, these motors possess a tertiary stereogenic centre on the upper half, characterised by a hydroxy group. Using a combination of femto- and nanosecond transient absorption spectroscopy, molecular dynamics simulations and low-temperature 1H NMR experiments we found that these motors operate similarly to push-pull second-generation overcrowded alkene-based molecular motors. Interestingly, the hydroxy group at the stereocentre enables a hydrogen bond with the carbonyl groups of the barbituric acid lower half, which drives a sub-picosecond excited-state isomerisation, as observed spectroscopically. Computational simulations predict an excited state “lasso” mechanism where the intramolecular hydrogen bond pulls the molecule towards the formation of the metastable state, with a high predicted quantum yield of isomerisation (68%) in gas phase.

U2 - 10.1039/d3sc03090c

DO - 10.1039/d3sc03090c

M3 - Article

AN - SCOPUS:85167368655

SN - 2041-6520

VL - 14

SP - 8458

EP - 8465

JO - Chemical Science

JF - Chemical Science

IS - 32

ER -

A visible-light-driven molecular motor based on barbituric acid

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CCDC 2269893: Experimental Crystal Structure Determination

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