Improving Fatigue Resistance of Dihydropyrene by Encapsulation within a Coordination Cage
Journal article, 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.

Author

Martina Canton

Weizmann Institute of Science

University of Bologna

Angela B. Grommet

Weizmann Institute of Science

Luca Pesce

University of Applied Sciences and Arts of Italian Switzerland (SUPSI)

Julius Gemen

Weizmann Institute of Science

Shiming Li

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry

Yael Diskin-Posner

Weizmann Institute of Science

Alberto Credi

University of Bologna

Giovanni M. Pavan

Polytechnic University of Turin

University of Applied Sciences and Arts of Italian Switzerland (SUPSI)

Joakim Andreasson

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry

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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Subject Categories

Polymer Chemistry

Biochemistry and Molecular Biology

Atom and Molecular Physics and Optics

Areas of Advance

Nanoscience and Nanotechnology (SO 2010-2017, EI 2018-)

DOI

10.1021/jacs.0c06146

PubMed

32791832

More information

Latest update

11/3/2020