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*

*Corresponding author for this work

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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 languageEnglish
Pages (from-to)8458-8465
Number of pages8
JournalChemical Science
Volume14
Issue number32
Early online date20-Jul-2023
DOIs
Publication statusPublished - 28-Aug-2023

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