Improving Fatigue Resistance of Dihydropyrene by Encapsulation within a Coordination Cage

Canton, Martina and Grommet, Angela B. and Pesce, Luca and Gemen, Julius and Li, Shiming and Diskin-Posner, Yael and Credi, Alberto and Pavan, Giovanni M. and Andréasson, Joakim and Klajn, Rafal (2020) Improving Fatigue Resistance of Dihydropyrene by Encapsulation within a Coordination Cage. Journal of the American Chemical Society, 142 (34). pp. 14557-14565. ISSN 0002-7863

Full text not available from this repository.


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 PdII6L4 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.

Actions (login required)

View Item View Item