Computational Investigation into Photoswitching Efficiency
of Diarylethene Derivatives: An Insight Based on the Decay Constant
of Electron Tunneling
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Abstract
The
switching efficiency (SE) of the intramolecular exchange interaction <i>J</i> between the open- and the closed-ring isomers of diarylethenes
(DAEs) was investigated using DFT calculations of DAE biradicals with
different core structures: DAEs with 3-thienyl, thiophene-<i>S</i>,<i>S</i>-dioxide-3-yl, 2-thienyl, or thiophene-<i>S</i>,<i>S</i>-dioxide-2-yl rings. The SE of DAE with
a 3-thienyl ring is calculated to be around 400-fold, which is the
largest among the four calculated DAEs. The decay constant β
of the exchange interaction <i>J</i> for the DAE molecular
wires was evaluated by calculating <i>J</i> for biradicals
with different lengths of wires. For the wires of the closed-ring
isomers of DAE with 3-thienyl- and thiophene-<i>S</i>,<i>S</i>-dioxide-3-yl rings, which are supposed to take a quinoid
structure, allyl nitronyl nitroxide radical was successfully employed.
The calculated β values showed a significant difference between
the open- and the closed-ring isomers, and this difference of β
is considered to be the origin of photoswitching of <i>J</i>. The difference of β upon isomerization, Δβ, is
in good agreement with SE, and the largest Δβ was obtained
for the DAE with a 3-thienyl ring. We can understand the switching
of <i>J</i> as the switching of electron tunneling efficiency
β between the open- and the closed-ring isomers