Volume 26, Issue 50 p. 11451-11461
Full Paper

Stimuli-Responsive Resorcin[4]arene Cavitands: Toward Visible-Light-Activated Molecular Grippers

Dr. Víctor García-López

Corresponding Author

Dr. Víctor García-López

Laboratory of Organic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zurich, HCI, Vladimir-Prelog-Weg 3, 8093 Zurich, Switzerland

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Dr. Michal Zalibera

Dr. Michal Zalibera

Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology, Radlinského 9, 81237 Bratislava, Slovakia

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Dr. Nils Trapp

Dr. Nils Trapp

Laboratory of Organic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zurich, HCI, Vladimir-Prelog-Weg 3, 8093 Zurich, Switzerland

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Dr. Martin Kuss-Petermann

Dr. Martin Kuss-Petermann

Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland

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Prof. Dr. Oliver S. Wenger

Prof. Dr. Oliver S. Wenger

Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland

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Prof. Dr. François Diederich

Corresponding Author

Prof. Dr. François Diederich

Laboratory of Organic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zurich, HCI, Vladimir-Prelog-Weg 3, 8093 Zurich, Switzerland

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First published: 11 August 2020
Citations: 7

Graphical Abstract

Kite in a vase: Resorcin[4]arene cavitands functionalized with an electron-accepting quinone and a [Ru(bpy)2dppz]2+ (bpy=2,2′-bipyridine, dppz=dipyrido[3,2-a:2′,3′-c]phenazine) photosensitizing wall can be switched upon visible-light irradiation between a flat kite in the quinone state Q and a vase conformation in the semiquinone radical anion state SQ. Conformational switching can also be triggered by changes in solvent or host–guest interactions.

Abstract

Resorcin[4]arene cavitands, equipped with diverse quinone (Q) and [Ru(bpy)2dppz]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)2dppz]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 CD3CN. 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.

Conflict of interest

The authors declare no conflict of interest.