TY - JOUR
T1 - Improving Fatigue Resistance of Dihydropyrene by Encapsulation within a Coordination Cage
AU - Canton, Martina
AU - Grommet, Angela B.
AU - Pesce, Luca
AU - Gemen, Julius
AU - Li, Shiming
AU - Diskin-Posner, Yael
AU - Credi, Alberto
AU - Pavan, Giovanni M.
AU - Andréasson, Joakim
AU - Klajn, Rafal
N1 - Funding Information:
We acknowledge funding from the European Union’s Horizon 2020 research and innovation program under the European Research Council (ERC) grant agreements 820008 (to R.K.), 818776 (to G.M.P.), and 692981 (to A.C.) and the Marie Skłodowska-Curie grant agreement no. 812868 (to J.G.), the Swedish Research Council VR (grant agreement 2016-03601 to J.A.), the Swiss National Science Foundation (grant agreement 200021_175735 to G.M.P.), and the Minerva Foundation with funding from the Federal German Ministry for Education and Research (R.K.). L.P. and G.M.P. acknowledge the computational resources provided by the Swiss National Supercomputing Center (CSCS). A.B.G. acknowledges funding from the Zuckerman STEM Leadership Program.
Publisher Copyright:
© 2020 American Chemical Society.
PY - 2020/8/26
Y1 - 2020/8/26
N2 - 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.
AB - 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.
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U2 - 10.1021/jacs.0c06146
DO - 10.1021/jacs.0c06146
M3 - Article
C2 - 32791832
AN - SCOPUS:85090068317
VL - 142
SP - 14557
EP - 14565
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 34
ER -