Catenane

1. Catenane • A Catenane is a mechanically-interlocked molecular architecture consisting of two or more interlocked macrocycles. They are analogous to bike chains or key rings in which the individual components are not directly connected, but the components cannot be separated without breaking one of the rings. Catenane is derived from the Latincatena meaning "chain". They are conceptually related to other mechanically-interlocked molecular architectures , such as rotaxanes, molecular knots or borromean ring. The synthesis of such entangled topologies has been made efficient through the combination of supramolecular chemistry with traditional covalent synthesis, however mechanically-interlocked molecular architectures have properties that differ from both “supramolecular assemblies” and “covalently-bonded molecules.” Recently the terminology "mechanical bond" has been coined to describe the connection between the components of a catenane.

2. Synthesis • There two primary approaches to the organic synthesis of catenanes. The first is to simply perform a ring closing reaction with the hope that some of the rings will form around other rings giving the desired catenane product. This so-called "statistical approach" lead to the first successful synthesis of a catenane, however the method suffers from very low yields. The second approach relies on preorganization of the macrocyclic precursors utilizing hydrogen bonding, metal coordination, hydrophobic forces, or coulombic interactions. These non-covalent interactions offset some of the entropic cost of association and help position the components to form the desired catenane upon the final ring-closing. This "template-directed" method has dramatically increased the yields that can be obtained for catenanes and thus has increased their potential for application. An example of this approach used bis-bipyridinium salts which form strong complexes threaded through crown ether bis(para-phenylene)-34-crown-10.

3. Families of Catenanes • There are a number of distinct methods of holding the precursors together prior to the ultimate ring-closing reaction in a template-directed catenane synthesis. Each noncovalent approach to catenane formation results in what can be considered different families of catenanes. • Another family of catenanes are called pretzelanes or bridged [2]catenanes after their likeness to pretzels with a spacer linking the two macrocycles. In one such system [1] one macrocycle is an electron deficient oligo Bis-bipyridinium ring and the other cycle is crown ethercyclophane based on paraphenylene or naphthalene. X-ray diffraction shows that due to pi-pi interactions the aromatic group of the cyclophane is held firmly inside the pyridinium ring. A limited number of (rapidly-interchanging) conformers exist for this type of compound.

4. Families of Catenanes Handcuff shaped catenane In handcuff-shaped catenanes [2], two connected rings are threaded through the same ring. The bis-macrocycle (red) contains two phenanthroline units in a crown ether chain. The interlocking ring is self-assembled when two more phenanthroline units with alkene arms coordinate through a copper(I) complex followed by a metathesis ring closing step.

5. References • Dynamic Chirality in Donor-Acceptor Pretzelanes Y. Liu, S. A. Vignon, X. Zhang, P. A. Bonvallet, S. I. Khan, K. N. Houk, and J. F. Stoddart J. Org. Chem.; 2005; 70(23) pp 9334 - 9344; (Article) DOI: 10.1021/jo051430g • A catenane consisting of a large ring threaded through both cyclic units of a handcuff-like compound Julien Frey, Tomá Kraus, Valérie Heitz and Jean-Pierre Sauvage Chemical Communications, 2005, (42), 5310 - 5312