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An Autocatalytic System of Photooxidation‐Driven Substitution Reactions on a FeII4L6 Cage Framework


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Authors

Neelakandan, Prakash P 
Jiménez, Azucena 
Thoburn, John D 
Nitschke, Jonathan R 

Abstract

jats:titleAbstract</jats:title>jats:pThe functions of life are accomplished by systems exhibiting nonlinear kinetics: autocatalysis, in particular, is integral to the signal amplification that allows for biological information processing. Novel synthetic autocatalytic systems provide a foundation for the design of artificial chemical networks capable of carrying out complex functions. Here we report a set of Fejats:supII</jats:sup>jats:sub4</jats:sub>Ljats:sub6</jats:sub> cages containing BODIPY chromophores having tuneable photosensitizing properties. Electron‐rich anilines were observed to displace electron‐deficient anilines at the dynamic‐covalent imine bonds of these cages. When iodoaniline residues were incorporated, heavy‐atom effects led to enhanced jats:sup1</jats:sup>Ojats:sub2</jats:sub> production. The incorporation of (methylthio)aniline residues into a cage allowed for the design of an autocatalytic system: oxidation of the methylthio groups into sulfoxides make them electron‐deficient and allows their displacement by iodoanilines, generating a better photocatalyst and accelerating the reaction.</jats:p>

Description

Keywords

self-assembly, metal-organic capsules, photosensitizers, autocatalysis

Journal Title

Angewandte Chemie

Conference Name

Journal ISSN

0044-8249
1521-3757

Volume Title

127

Publisher

Wiley
Sponsorship
Engineering and Physical Sciences Research Council (EP/I005447/1)
European Research Council (259352)
This work was funded by the European Research Council (259352).