Light Driven Ultrafast Bioinspired Molecular Motors: Steering and Accelerating Photoisomerization Dynamics of Retinal

Publikation: Bidrag til tidsskriftTidsskriftartikelfagfællebedømt

  • Elisabeth Gruber
  • Adil M. Kabylda
  • Nielsen, Mogens Brøndsted
  • Anne P. Rasmussen
  • Ricky Teiwes
  • Pavel A. Kusochek
  • Anastasia V. Bochenkova
  • Lars H. Andersen

Photoisomerization of retinal protonated Schiff base in microbial and animal rhodopsins are strikingly ultrafast and highly specific. Both protein environments provide conditions for fine-tuning the photochemistry of their chromophores. Here, by combining time-resolved action absorption spectroscopy and high-level electronic structure theory, we show that similar control can be gained in a synthetically engineered retinal chromophore. By locking the dimethylated retinal Schiff base at the C11═C12 double bond in its trans configuration (L-RSB), the excited-state decay is rendered from a slow picosecond to an ultrafast subpicosecond regime in the gas phase. Steric hindrance and pretwisting of L-RSB are found to be important for a significant reduction in the excited-state energy barriers, where isomerization of the locked chromophore proceeds along C9═C10 rather than the preferred C11═C12 isomerization path. Remarkably, the accelerated excited-state dynamics also becomes steered. We show that L-RSB is capable of unidirectional 360° rotation from all-trans to 9-cis and from 9-cis to all-trans in only two distinct steps induced by consecutive absorption of two 600 nm photons. This opens a way for the rational design of red-light-driven ultrafast molecular rotary motors based on locked retinal chromophores.

OriginalsprogEngelsk
TidsskriftJournal of the American Chemical Society
Vol/bind144
Udgave nummer1
Sider (fra-til)5
Antal sider69
ISSN0002-7863
DOI
StatusUdgivet - 2022

Bibliografisk note

Funding Information:
The work is supported by the Russian Science Foundation (grant no. 17-13-01276) and by a grant (17512) from VILLUM FONDEN. The calculations were carried out using the equipment of the shared research facilities of HPC computing resources at Lomonosov Moscow State University as well as the local resources provided through the Lomonosov Moscow State University Program of Development.

Publisher Copyright:
© 2021 American Chemical Society

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