Organic Letters
Letter
thank Ms. Ayako Tohzaka of Okayama University for fruitful
discussions.
Table 2. Fluorescence Quantum Yields, Lifetimes, and
Kinetic Constants of cis-ABPX Dyes
dye
ϕfl
τobs [ns]
kf [ns−1
]
knr [ns−1
]
REFERENCES
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ABPX01 1a
0.17
0.70
0.50
0.55
0.72
2.34
2.48
2.41
0.24
0.30
0.20
0.23
1.06
0.30
0.32
0.32
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ABPX101 10a
ABPX102 16a
ABPX103 21a
Whereas the intermolecular rotations of the diethylamino
chains of 1a increased the nonradiative transition probability,
reduction of the xanthene moiety mobility was achieved by the
inclusion of rigid six-membered rings in ABPX101H2
2+
−
103H22+, which resulted in the drastic enhancement of ϕfl. In
addition, the ϕfl of 10a was higher than that of 16a. This would
be because the torsional motion of the carboxylic benzene
moieties was suppressed by the internal steric hindrance caused
by the attachment of the carboxylic benzene moieties to the
proximate dimethyl of ABPX101. These results showed that
RIM played a dominant role in creating the nonradiative
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ABPX dyes.
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In conclusion, we have developed the first highly fluorescent
ABPX dyes in the red and NIR regions since the ABPX dye was
first reported by our group.8 The rigid conjugation of the
xanthene moiety in the ABPX dyes resulted in high
fluorescence quantum yields. ABPX dyes are alternative π-
conjugated organic molecules that can be dissolved in
commonly used solvents. Our findings demonstrate that
ABPX dyes have the potential to act as a substitute for or a
complement to existing commercially available fluorescence
dyes for use as a new standard for various applications, such as
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ASSOCIATED CONTENT
* Supporting Information
Experimental procedures, spectrofluorometric and -photo-
metric spectra, and additional photophysical data for ABPX
dyes. This material is available free of charge via the Internet at
■
S
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AUTHOR INFORMATION
Corresponding Authors
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
(12) Sauers, R. R.; Husain, S. N.; Piechowski, A. P.; Bird, G. R. Dyes
Pigment. 1987, 7, 35.
This work was supported by the Adaptable and Seamless
Technology Transfer Program through Target-driven R&D
(Grant AS242Z01483M) of Japan Science and Technology
(JST). This research was also supported in part by a Grant-in-
Aid for Challenging Exploratory Research (Grant 24659019)
from the Ministry of Education, Culture, Sports, Science and
Technology (MEXT) of the Japan Society for the Promotion of
Science (JSPS). We thank Dr. Hiroyuki Koshino of RIKEN for
NMR measurement and Dr. Yayoi Hongo and Dr. Takemichi
Nakamura of RIKEN for MS measurement. We would also like
to thank Dr. Toshihiro Shirasaki of Hitachi High-Tech Science
Co., Ltd. for support on fluorescence emission analysis. We also
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dx.doi.org/10.1021/ol403262x | Org. Lett. 2014, 16, 258−261