Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 27, Issue 43, Pages 11019-11020Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202102101
Keywords
azobenzene; molecular machine; non-equilibrium process; photochemistry; rotaxanes
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Funding
- ERC
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The article describes a system of pseudorotaxanes in which photon input triggers unidirectional motion of a macrocyclic ring with respect to a non-symmetric molecular axle, validating the photoinduced energy ratcheting mechanism. Fine changes in the axle structure were shown to improve motor performance. The design highlights the modularity and versatility, providing easy access to dynamic systems operating under photoinduced non-equilibrium regimes.
The development of artificial nanoscale motors that can use energy from a source to perform tasks requires systems capable of performing directionally controlled molecular movements and operating away from chemical equilibrium. Here, the design, synthesis and properties of pseudorotaxanes are described, in which a photon input triggers the unidirectional motion of a macrocyclic ring with respect to a non-symmetric molecular axle. The photoinduced energy ratcheting at the basis of the pumping mechanism is validated by measuring the relevant thermodynamic and kinetic parameters. Owing to the photochemical behavior of the azobenzene moiety embedded in the axle, the pump can repeat its operation cycle autonomously under continuous illumination. NMR spectroscopy was used to observe the dissipative non-equilibrium state generated in situ by light irradiation. We also show that fine changes in the axle structure lead to an improvement in the performance of the motor. Such results highlight the modularity and versatility of this minimalist pump design, which provides facile access to dynamic systems that operate under photoinduced non-equilibrium regimes.
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