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An Autocatalytic System of Photooxidation‐Driven Substitution Reactions on a Fe II 4 L 6 Cage Framework
Author(s) -
Neelakandan Prakash P.,
Jiménez Azucena,
Thoburn John D.,
Nitschke Jonathan R.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201507045
Subject(s) - autocatalysis , aniline , chemistry , imine , covalent bond , photochemistry , chromophore , combinatorial chemistry , catalysis , organic chemistry
The 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 Fe II 4 L 6 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 1 O 2 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.