Chemically optimising operational efficiency of molecular rotary motors

Conyard, Jamie, Cnossen, Arjen, Browne, Wesley R., Feringa, Ben L. and Meech, Steve (2014) Chemically optimising operational efficiency of molecular rotary motors. Journal of the American Chemical Society, 136 (27). pp. 9692-9700. ISSN 0002-7863

Microsoft Word (Molec Motor R dep paper for resub 11-6) - Draft Version Download (1MB)

Abstract

Unidirectional molecular rotary motors that harness photoinduced cis–trans (E–Z) isomerization are promising tools for the conversion of light energy to mechanical motion in nanoscale molecular machines. Considerable progress has been made in optimizing the frequency of ground-state rotation, but less attention has been focused on excited-state processes. Here the excited-state dynamics of a molecular motor with electron donor and acceptor substituents located to modify the excited-state reaction coordinate, without altering its stereochemistry, are studied. The substituents are shown to modify the photochemical yield of the isomerization without altering the motor frequency. By combining 50 fs resolution time-resolved fluorescence with ultrafast transient absorption spectroscopy the underlying excited-state dynamics are characterized. The Franck–Condon excited state relaxes in a few hundred femtoseconds to populate a lower energy dark state by a pathway that utilizes a volume conserving structural change. This is assigned to pyramidalization at a carbon atom of the isomerizing bridging double bond. The structure and energy of the dark state thus reached are a function of the substituent, with electron-withdrawing groups yielding a lower energy longer lived dark state. The dark state is coupled to the Franck–Condon state and decays on a picosecond time scale via a coordinate that is sensitive to solvent friction, such as rotation about the bridging bond. Neither subpicosecond nor picosecond dynamics are sensitive to solvent polarity, suggesting that intramolecular charge transfer and solvation are not key driving forces for the rate of the reaction. Instead steric factors and medium friction determine the reaction pathway, with the sterically remote substitution primarily influencing the energetics. Thus, these data indicate a chemical method of optimizing the efficiency of operation of these molecular motors without modifying their overall rotational frequency.

Item Type:	Article
Faculty \ School:	Faculty of Science > School of Chemistry (former - to 2024)
UEA Research Groups:	Faculty of Science > Research Groups > Physical and Analytical Chemistry (former - to 2017) Faculty of Science > Research Groups > Chemistry of Light and Energy Faculty of Science > Research Groups > Centre for Photonics and Quantum Science
Depositing User:	Pure Connector
Date Deposited:	18 Nov 2014 13:34
Last Modified:	28 Mar 2025 06:17
URI:	https://ueaeprints.uea.ac.uk/id/eprint/51034
DOI:	10.1021/ja5041368

Downloads

Actions (login required)

View Item