Catenanes - molecules consisting of interlocked macrocyclic rings - have been prepared by templation strategies for some thirty years. The utilization of Cu(I) cation, aromatic donor-acceptor interactions and hydrogen bonding assisted self-assembly strategies has led to the construction of numerous examples of these aesthetically pleasing species. This review seeks to discuss key developments in the synthesis and functional application of catenanes that have occurred since the Millennium. The much expanded range of metal cation templates; the genesis and growth of anion templation, as well as the use of alternative supramolecular interactions (halogen bonding and radical templation) and thermodynamically controlled reactions to synthesize catenanes are detailed. The class of catenanes that may be described as "molecular machines" are then highlighted and to conclude, attempts to fabricate catenanes onto surfaces and into metal organic frameworks (MOFs) are discussed.
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http://dx.doi.org/10.1039/c4cs00029c | DOI Listing |
Chem Commun (Camb)
January 2025
Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands.
A [2]catenane-based receptor functionalized with stiff-stilbene can be reversibly switched with 340/385 nm light between its - and -isomers, which leads to a considerable change in chloride binding affinity. Photoisomerization in the presence of chloride allows for on demand guest uptake and release.
View Article and Find Full Text PDFChem Rev
January 2025
Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
Template-directed synthesis has become a powerful methodology to access complex molecules. Noncovalent templating has been widely used in the last few decades, but less attention has been paid to covalent template-directed synthesis, despite the fact that this methodology was used for the first reported synthesis of a catenane. This review highlights the evolution of covalent templating over the last 60 years, thereby providing a toolbox for the design of efficient covalent templating processes.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
TU Dortmund University, Faculty for Chemistry and Chemical Biology, Otto-Hahn-Str. 6, 44227, Dortmund, GERMANY.
Precise control over the catenation process in interlocked supramolecular systems remains a significant challenge. Here, we report a system in which a lantern-shaped Pd2L4 cage can dimerize to form two distinct Pd4L8 catenanes with different interlocking degree: a previously described quadruply interlocked double cage motif of D4 symmetry and an unprecedented triply interlocked structure of C2h symmetry. While the former structure features a linear arrangement of four Pd(II) centers, separated by three mechanically linked pockets, the new motif has a staggered shape.
View Article and Find Full Text PDFAngew 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.
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