Improving Fatigue Resistance of Dihydropyrene by Encapsulation within a Coordination Cage
Artikel i vetenskaplig tidskrift, 2020

Photochromic molecules undergo reversible isomerization upon irradiation with light at different wavelengths, a process that can alter their physical and chemical properties. For instance, dihydropyrene (DHP) is a deep-colored compound that isomerizes to light-brown cyclophanediene (CPD) upon irradiation with visible light. CPD can then isomerize back to DHP upon irradiation with UV light or thermally in the dark. Conversion between DHP and CPD is thought to proceed via a biradical intermediate; bimolecular events involving this unstable intermediate thus result in rapid decomposition and poor cycling performance. Here, we show that the reversible isomerization of DHP can be stabilized upon confinement within a (PdIIL4)-L-6 coordination cage. By protecting this reactive intermediate using the cage, each isomerization reaction proceeds to higher yield, which significantly decreases the fatigue experienced by the system upon repeated photocycling. Although molecular confinement is known to help stabilize reactive species, this effect is not typically employed to protect reactive intermediates and thus improve reaction yields. We envisage that performing reactions under confinement will not only improve the cyclic performance of photochromic molecules, but may also increase the amount of product obtainable from traditionally low-yielding organic reactions.


Martina Canton

Weizmann Institute of Science

Universita di Bologna

Angela Beth Grommet

Weizmann Institute of Science

Luca Pesce

Scuola Universitaria Professionale della Svizzera Italiana (SUPSI)

Julius Gemen

Weizmann Institute of Science

Shiming Li

Chalmers, Kemi och kemiteknik, Kemi och biokemi

Yael Diskin-Posner

Weizmann Institute of Science

Alberto Credi

Universita di Bologna

Giovanni M. Pavan

Politecnico di Torino

Scuola Universitaria Professionale della Svizzera Italiana (SUPSI)

Joakim Andreasson

Chalmers, Kemi och kemiteknik, Kemi och biokemi

Rafal Klajn

Weizmann Institute of Science

Journal of the American Chemical Society

0002-7863 (ISSN) 1520-5126 (eISSN)

Vol. 142 34 14557-14565

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