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COMMUNICATION
Journal Name
Notes and references
DOI: 10.1039/C6CC09600J
§
Since (Z)-2 has a slightly larger oxidation potential than (E)-2
†
(see Table S8 in ESI ), this process should be however
thermodynamically disfavored.
1
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3
Fig. 3 Mechanism proposed for the photocatalytic isomerization of
(Z)-
2 on AuNP@1.
caused owing to the nonnegligible energy barrier computed,
+
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and (c) subsequent reduction of (E)-
surface (or by interaction with a free (Z)-
2
at the nanoparticle
molecule§) to render
2
the final neutral product of the reaction. It must be noted that
this mechanism is only applicable to low-Eox stilbenes such as
2
. However, an analogous photocatalytic scheme evolving
through electron injection and isomerization of the resulting
radical anion could occur for electron-poor derivatives, which
might explain why slightly larger photo-catalytic efficiencies
were measured for (Z)-
4 with respect to (Z)-3 despite
presenting lower association constants with -CD.
To corroborate the mechanism proposed in Fig. 3, further
experiments were performed with (Z)-4-hydroxy stilbene ((Z)-
5
), another stilbene derivative with low Eox, high thermal
isomerization barrier and capable to supramolecularly interact
with -CD (Tables S1, S7 and S8 in ESI†). Large photocatalytic
6
7
Z
E conversion with AuNP@
Table S4 in ESI†), thus supporting the reaction scheme devised
for electron-rich stilbenes. Actually, nonnegligible (Z)-
1 was also measured for 5 (88%,
5
isomerization was observed by effect of AuNP@1 even in the
dark (17%, Table S4 in ESI†), which hints for a stronger catalyst-
substrate interaction in this case that might explain the larger
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photocatalytic efficiency observed with respect to (Z)-2.
In summary, a new strategy for plasmon-based catalysis
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visible light, obtaining in some cases better yields than under
direct UV excitation. As revealed by theoretical calculations
and electrochemical measurements, such large photocatalytic
activity results from the combined action of hole charge
injection and photothermal effects caused by AuNPs.
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This work was supported by projects CTQ2015-65439-R
and CTQ2014-59544-P from the MINECO/FEDER. M. P. and F.
P. thank the Universitat Autònoma de Barcelona for a
predoctoral PIF fellowship. M. S. gratefully acknowledges
support from the ICREA Academia award. X.S.M is indebted for
the Professor Agregat Serra Húnter position.
4 | J. Name., 2012, 00, 1-3
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