Ternary host-guest complexes with rapid exchange kinetics and photoswitchable fluorescence

Julius Gemen; Michał J Białek; Miri Kazes; Linda J W Shimon; Moran Feller; Sergey N Semenov; Yael Diskin-Posner; Dan Oron; Rafal Klajn

doi:10.1016/j.chempr.2022.05.008

Ternary host-guest complexes with rapid exchange kinetics and photoswitchable fluorescence

Julius Gemen, Michał J Białek, Miri Kazes, Linda J W Shimon, Moran Feller, Sergey N Semenov, Yael Diskin-Posner, Dan Oron, Rafal Klajn^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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Abstract

Confinement within molecular cages can dramatically modify the physicochemical properties of the encapsulated guest molecules, but such host-guest complexes have mainly been studied in a static context. Combining confinement effects with fast guest exchange kinetics could pave the way toward stimuli-responsive supramolecular systems—and ultimately materials—whose desired properties could be tailored “on demand” rapidly and reversibly. Here, we demonstrate rapid guest exchange between inclusion complexes of an open-window coordination cage that can simultaneously accommodate two guest molecules. Working with two types of guests, anthracene derivatives and BODIPY dyes, we show that the former can substantially modify the optical properties of the latter upon noncovalent heterodimer formation. We also studied the light-induced covalent dimerization of encapsulated anthracenes and found large effects of confinement on reaction rates. By coupling the photodimerization with the rapid guest exchange, we developed a new way to modulate fluorescence using external irradiation.

Original language	English
Pages (from-to)	2362-2379
Number of pages	18
Journal	Chem
Volume	8
Issue number	9
DOIs	https://doi.org/10.1016/j.chempr.2022.05.008
Publication status	Published - 8 Sept 2022

Funding

We acknowledge funding from the European Union’s Horizon 2020 Research and Innovation Program under the European Research Council (ERC) grant agreement no. 820008 and the Marie Skłodowska-Curie grant agreement no. 812868. This research was supported in part by the “Excellence Initiative – Research University” program at the University of Wrocław. DFT calculations were carried out using resources provided by the Wrocław Center for Networking and Supercomputing, grant 329. We gratefully acknowledge Dr. Miłosz Siczek (Department of Chemistry, University of Wrocław) for collecting X-ray crystallographic data for (a3)2⊂C and (a2⋅b1)⊂C and Dr. Alla Falkovich (Department of Chemical Research Support, Weizmann Institute of Science) for assistance with mass spectrometry measurements. Author contributions J.G. and R.K. conceived the study and designed the experiments. J.G. and M.J.B. performed the experiments. M.J.B., L.J.W.S., and Y.D.-P. determined the X-ray structures of the inclusion complexes. J.G. and M.K. performed the transient spectroscopy experiments. J.G., M.K., and D.O. analyzed the results of the transient spectroscopy experiments. M.J.B. carried out the DFT calculations. S.N.S. derived the kinetic rate equations. J.G. and R.K. wrote the manuscript. All authors discussed the results and commented on the manuscript.

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title = "Ternary host-guest complexes with rapid exchange kinetics and photoswitchable fluorescence",

abstract = "Confinement within molecular cages can dramatically modify the physicochemical properties of the encapsulated guest molecules, but such host-guest complexes have mainly been studied in a static context. Combining confinement effects with fast guest exchange kinetics could pave the way toward stimuli-responsive supramolecular systems—and ultimately materials—whose desired properties could be tailored “on demand” rapidly and reversibly. Here, we demonstrate rapid guest exchange between inclusion complexes of an open-window coordination cage that can simultaneously accommodate two guest molecules. Working with two types of guests, anthracene derivatives and BODIPY dyes, we show that the former can substantially modify the optical properties of the latter upon noncovalent heterodimer formation. We also studied the light-induced covalent dimerization of encapsulated anthracenes and found large effects of confinement on reaction rates. By coupling the photodimerization with the rapid guest exchange, we developed a new way to modulate fluorescence using external irradiation.",

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AU - Gemen, Julius

AU - Białek, Michał J

AU - Kazes, Miri

AU - Shimon, Linda J W

AU - Feller, Moran

AU - Semenov, Sergey N

AU - Diskin-Posner, Yael

AU - Oron, Dan

AU - Klajn, Rafal

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N2 - Confinement within molecular cages can dramatically modify the physicochemical properties of the encapsulated guest molecules, but such host-guest complexes have mainly been studied in a static context. Combining confinement effects with fast guest exchange kinetics could pave the way toward stimuli-responsive supramolecular systems—and ultimately materials—whose desired properties could be tailored “on demand” rapidly and reversibly. Here, we demonstrate rapid guest exchange between inclusion complexes of an open-window coordination cage that can simultaneously accommodate two guest molecules. Working with two types of guests, anthracene derivatives and BODIPY dyes, we show that the former can substantially modify the optical properties of the latter upon noncovalent heterodimer formation. We also studied the light-induced covalent dimerization of encapsulated anthracenes and found large effects of confinement on reaction rates. By coupling the photodimerization with the rapid guest exchange, we developed a new way to modulate fluorescence using external irradiation.

AB - Confinement within molecular cages can dramatically modify the physicochemical properties of the encapsulated guest molecules, but such host-guest complexes have mainly been studied in a static context. Combining confinement effects with fast guest exchange kinetics could pave the way toward stimuli-responsive supramolecular systems—and ultimately materials—whose desired properties could be tailored “on demand” rapidly and reversibly. Here, we demonstrate rapid guest exchange between inclusion complexes of an open-window coordination cage that can simultaneously accommodate two guest molecules. Working with two types of guests, anthracene derivatives and BODIPY dyes, we show that the former can substantially modify the optical properties of the latter upon noncovalent heterodimer formation. We also studied the light-induced covalent dimerization of encapsulated anthracenes and found large effects of confinement on reaction rates. By coupling the photodimerization with the rapid guest exchange, we developed a new way to modulate fluorescence using external irradiation.

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Ternary host-guest complexes with rapid exchange kinetics and photoswitchable fluorescence

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