OFF–ON Fluorescence Sensing of Fluoride by
Donor–Antimony(V) Lewis Acids
Posted on 2017-12-14 - 19:37
A series of triarylmethylstibonium
Lewis acids of general formula
[Ph2MeSb-(p-(C6H4))-FLUO]+ bearing a peripheral electron-rich fluorophore
(FLUO = 10H-phenoxazine ([3a]+), diphenylamine ([3b]+), and 9H-carbazole ([3c]+)) have been synthesized
and investigated for the fluorescence turn-on sensing of fluoride
anions. Treatment of the stibonium cations with fluoride anions leads
to the corresponding fluorostiboranes (3a-F–3c-F). While the stibonium cations are almost nonemissive,
the fluorostiboranes display fluorophore-centered emissions arising
from the corresponding π–π* excited state. The
carbazole-containing derivative [3c]+ exhibits
the most intense fluorescence turn-on response. It also displays a
high binding constant (K > 107 M–1) in MeCN and shows compatibility with protic media
such as MeOH
(K = 950(±50) M–1). Computational
studies aimed at identifying the origin of the turn-on response show
that the excited state of the stibonium cations is best described
as charge transfer in nature with the π system of the fluorophore
acting as the donor and the π*−σ* system of the
stibonium unit acting as the acceptor. This π(FLUO)−π*/σ*(Ph2MeSb-(p-(C6H4))) excited
state is nonemissive, making these cations dark in the absence of
fluoride anions. Conversion to the fluorostiboranes occurs via donation
of a fluoride lone pair into the antimony-centered σ*. Formation
of this Sb–F bond modifies the electronic structure of the
platform and restores the emissive π–π* excited
state of the fluorophore, thus accounting for the observed OFF–ON
fluorescence response.
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Kumar, Ajay; Yang, Mengxi; Kim, Minji; Gabbaï, François P.; Lee, Min Hyung (2017). OFF–ON Fluorescence Sensing of Fluoride by
Donor–Antimony(V) Lewis Acids. ACS Publications. Collection. https://doi.org/10.1021/acs.organomet.7b00759
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AUTHORS (5)
AK
Ajay Kumar
MY
Mengxi Yang
MK
Minji Kim
FG
François P. Gabbaï
ML
Min Hyung Lee