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Stimuli‐Responsive Resorcin[4]arene Cavitands: Toward Visible‐Light‐Activated Molecular Grippers
Author(s) -
GarcíaLópez Víctor,
Zalibera Michal,
Trapp Nils,
KussPetermann Martin,
Wenger Oliver S.,
Diederich François
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202001788
Subject(s) - phenazine , chemistry , photochemistry , cyclohexane , electron transfer , bipyridine , electrochemistry , quinone , stereochemistry , crystallography , electrode , organic chemistry , crystal structure
Resorcin[4]arene cavitands, equipped with diverse quinone ( Q ) and [Ru(bpy) 2 dppz] 2+ (bpy=2,2′‐bipyridine, dppz=dipyrido[3,2‐ a :2′,3′‐ c ]phenazine) photosensitizing walls in different configurations, were synthesized. Upon visible‐light irradiation at 420 nm, electron transfer from the [Ru(bpy) 2 dppz] 2+ to the Q generates the semiquinone ( SQ ) radical anion, triggering a large conformational switching from a flat kite to a vase with a cavity for the encapsulation of small guests, such as cyclohexane and heteroalicyclic derivatives, in CD 3 CN. Depending on the molecular design, the SQ radical anion can live for several minutes (≈10 min) and the vase can be generated in a secondary process without need for addition of a sacrificial electron donor to accumulate the SQ state. Switching can also be triggered by other stimuli, such as changes in solvent, host–guest complexation, and chemical and electrochemical processes. This comprehensive investigation benefits the development of stimuli‐responsive nanodevices, such as light‐activated molecular grippers.