Transition metal-containing catenanes and rotaxanes are ideally suited to build molecular machines and motors; in the present review article, three examples from our group are discussed which consist of (i) a fast-moving electrochemically-driven pirouetting machine, (ii) a linear rotaxane dimer whose behaviour is reminiscent of muscles, in the sense that it can be stretched or contracted and (iii) a light-driven machine consisting of a catenane constructed around a ruthenium(II) centre.
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http://dx.doi.org/10.1039/b500680p | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Henan University, Colleg of Chemistry and Molecular Sciences, Jingmin, 475004, Kaifeng, CHINA.
Cycloparaphenylenes (CPPs) represent a significant challenge for the synthesis of mechanically interlocked architectures, because they lack heteroatoms, which precludes traditional active and passive template methods. To circumvent this problem and explore the fundamental and functional properties of CPP rotaxanes and catenanes, researches have resorted to unusual non-covalent and even to labor-intensive covalent template approaches. Herein, we report a ring-in-ring non-covalent template strategy that makes use of the surprisingly strong non-covalent inclusion of crown ethers into suitably sized CPPs.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China.
Macrocycles represent one important class of functional molecules, and dynamic macrocycles with the potential of cleavability, adaptability, and topological conversion are challenging. Herein we report photoswitchable allosteric and topological control of dynamic covalent macrocycles and further the use in guest binding and mechanically interlocked molecules. The manipulation of competing ring-chain equilibria and bond formation/scission within reaction systems enabled light-induced structural regulation over dithioacetal and thioacetal dynamic bonds, accordingly realizing bidirectional switching between crown ether-like covalent macrocycles and their linear counterparts.
View Article and Find Full Text PDFChem Commun (Camb)
October 2024
Department of Chemistry, Lancaster University, Lancaster, LA1 4YB, UK.
The synthesis and characterization of the first examples of cubane containing interlocked molecules are reported. Catenanes and rotaxanes have been prepared by hydrogen bond templation with cubane-1,3-dicarboxamides replacing isophthalamide motifs.
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia.
Stereoisomerism, stemming from the spatial orientation of components in molecular structures, plays a decisive role in nature. While the unconventional bonding found in mechanically interlocked molecules gives rise to unique expressions of stereochemistry, the exploration of their stereoisomers is still in its infancy. Sequence isomerism, characterized by variations in the ordering of mechanically interlocked components in catenanes and rotaxanes, mirrors the sequence variations found in biological macromolecules.
View Article and Find Full Text PDFChem Commun (Camb)
October 2024
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford OX1 3TA, UK.
The ever-increasing interest directed towards the construction of host architectures capable of the strong and selective recognition of various ionic species of biological, medical and environmental importance has identified mechanically interlocked molecules (MIMs), such as rotaxanes and catenanes, as potent host systems, owing to their unique three-dimensional topologically preorganised cavity recognition environments. Ion-pair receptors are steadily gaining prominence over monotopic receptor analogues due to their enhanced binding strength and selectivity, demonstrated primarily through acyclic and macrocyclic heteroditopic host systems. Exploiting the mechanical bond for ion-pair recognition through the strategic design of neutral heteroditopic MIMs offers exciting opportunities to accomplish potent and effective binding while mitigating competing interactions from the bulk solvent and counter-ions.
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