TY - JOUR
T1 - Light Driven Ultrafast Bioinspired Molecular Motors
T2 - Steering and Accelerating Photoisomerization Dynamics of Retinal
AU - Gruber, Elisabeth
AU - Kabylda, Adil M.
AU - Nielsen, Mogens Brøndsted
AU - Rasmussen, Anne P.
AU - Teiwes, Ricky
AU - Kusochek, Pavel A.
AU - Bochenkova, Anastasia V.
AU - Andersen, Lars H.
N1 - Publisher Copyright:
© 2021 American Chemical Society.
PY - 2022/1/12
Y1 - 2022/1/12
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85122207922&partnerID=8YFLogxK
U2 - 10.1021/jacs.1c10752
DO - 10.1021/jacs.1c10752
M3 - Journal article
C2 - 34958197
AN - SCOPUS:85122207922
SN - 0002-7863
VL - 144
SP - 69
EP - 73
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 1
ER -