Mastering the non-equilibrium assembly and operation of molecular machines

Cristian Pezzato, Chuyang Cheng, J. Fraser Stoddart*, R. Dean Astumian

*Corresponding author for this work

Research output: Contribution to journalReview articlepeer-review

204 Scopus citations


In mechanically interlocked compounds, such as rotaxanes and catenanes, the molecules are held together by mechanical rather than chemical bonds. These compounds can be engineered to have several well-defined mechanical states by incorporating recognition sites between the different components. The rates of the transitions between the recognition sites can be controlled by introducing steric "speed bumps" or electrostatically switchable gates. A mechanism for the absorption of energy can also be included by adding photoactive, catalytically active, or redox-active recognition sites, or even charges and dipoles. At equilibrium, these Mechanically Interlocked Molecules (MIMs) undergo thermally activated transitions continuously between their different mechanical states where every transition is as likely as its microscopic reverse. External energy, for example, light, external modulation of the chemical and/or physical environment or catalysis of an exergonic reaction, drives the system away from equilibrium. The absorption of energy from these processes can be used to favour some, and suppress other, transitions so that completion of a mechanical cycle in a direction in which work is done on the environment-the requisite of a molecular machine-is more likely than completion in a direction in which work is absorbed from the environment. In this Tutorial Review, we discuss the different design principles by which molecular machines can be engineered to use different sources of energy to carry out self-organization and the performance of work in their environments.

Original languageEnglish (US)
Pages (from-to)5491-5507
Number of pages17
JournalChemical Society Reviews
Issue number18
StatePublished - Sep 21 2017

ASJC Scopus subject areas

  • General Chemistry


Dive into the research topics of 'Mastering the non-equilibrium assembly and operation of molecular machines'. Together they form a unique fingerprint.

Cite this