Chirality‐Driven Self‐Assembly of Discrete, Homochiral FeII2L3 Cages. Issue 23 (15th March 2023)

• Record Type: Journal Article
• Authors: Sun, Bin; Meeus, Eva J.; de Zwart, Felix J.; Bobylev, Eduard O.; Mooibroek, Tiddo J.; Mathew, Simon; Reek, Joost N. H.
• Is Part Of: Chemistry. Volume 29:Issue 23(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-03-15
• Subjects: Supramolecular chemistry -- Self-assembly -- Self-sorting -- Iron -- M2L3 cage; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202203900
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Coordination chemistry is a powerful method to synthesize supramolecular cages with distinct features that suit specific applications. This work demonstrates the synthesis of discrete, homochiral Fe II 2 L3 cages via chirality‐driven self‐assembly. Specifically, the installation of chirality – at both the vertices and ligand backbones – allows the formation of discrete, homochiral Fe II 2 L3 cages of different sizes via stereochemical control of the iron(II) centers. We observed that larger cages require multiple chiral centra (chiral ligands and vertices). In contrast, the formation of smaller cages is stereoselective with solely chiral ligands. The latter cages can also be formed from two chiral subcomponents, but only when they have matching chirality. Single‐crystal X‐ray diffraction of these smaller Fe II 2 L3 cages revealed several non‐covalent interactions as a driving force for narcissistic chiral self‐sorting. This expected behavior was confirmed utilizing the shorter ligands in racemic form, yielding discrete, homochiral Fe II 2 L3 cages formed in enantiomeric pairs. Abstract : What does it take to make Homochiral Cages by sub‐component Self‐Assembly? If the cage is small enough, only limited number of chiral ligands are required because of communication by non‐covalent interactions, which also results in narcissistic chiral self‐sorting behavior.