4.6 Article

Artificial Supramolecular Pumps Powered by Light

Journal

CHEMISTRY-A EUROPEAN JOURNAL
Volume 27, Issue 43, Pages 11076-11083

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202101163

Keywords

azobenzene; molecular machine; non-equilibrium process; photochemistry; rotaxanes

Funding

  1. EU (H2020 ERC AdG) [692981]
  2. Ministero dell'Universita e della Ricerca [PRIN 20173L7W8K, 201732PY3X, FARE R16S9XXKX3]

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This study describes the design, synthesis, and properties of pseudorotaxanes, with a focus on the photoinduced energy ratcheting at the basis of the pumping mechanism. Using NMR spectroscopy, the dissipative non-equilibrium state generated by light irradiation was observed. Additionally, fine changes in the axle structure were shown to improve the performance of the motor, highlighting the modularity and versatility of this minimalist pump design.
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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