M. Brellier et al. / Tetrahedron Letters 51 (2010) 1269–1272
1271
RO2C
N
O
O
CO2R
N
H
N
H
N
RO2C
RO2C
5 N
H
N
H
5
2
CO R
O
4
4
O
O
CO2R
O
N
O
N
N
O
NH
O
a)
B
F2
N
N
B
F2
10
R = Bn : 13
R = H : 2
b)
Scheme 2. Chemical synthesis of dye 2. Reagents and conditions: (a) DCM, DIPEA, 5, rt, 18 h, 70%; (b) EtOH, Pd/C (10%, w/w), rt, 4 h, 57%.
Table 1
Spectroscopic properties of fluorescent BODIPYs
max(abs) ±0.25a (nm)
k
max(em) ±0.5a (nm)
Stokes shift
D
m
(cm
ꢁ1
)
U
exp ±0.02
b
s (ns) ±0.05
Dye
Solvent
k
3
CHCl
CHCl
CHCl
CHCl
3
3
3
3
529.5
531.25
529.0
529.5
523.75
524
544
504
625
538
504
574
565
591
634
0.73
0.58
0.80
0.74
0.79
0.34
0.53
0.28
4.85
4.40
5.10
5.00
5.30
5.15
5.25
5.50
1
1
1
0
1
3
1
2
1
2
549.5
544.5
544
540
540
MeOH
MeOH
c
H
H
2
O
O
524.25
524
541
542
c
2
a
b
c
Determined at a 2
l
M concentration in the indicated solvent.
23
Rhodamine 6G in ethanol was used as standard at 20 °C.
5 mM phosphate-citrate buffer, pH 7.0.
1
pared with those recorded in MeOH, except for the quantum yield exp
which decreased slightly, while maintaining a high value for the
References and notes
1
2
.
.
Treibs, A.; Kreuzer, F.-H. Justus Liebigs Ann. Chem. 1968, 718, 208–223.
(a) Kumaresan, D.; Thummel, R. P.; Bura, T.; Ulrich, G.; Ziessel, R. Chem. Eur. J.
009, 15, 6335–6339; (b) Harriman, A.; Mallon, L. J.; Ulrich, G.; Ziessel, R. Chem.
fluorescence lifetime
s. Few photophysical properties of hepta-
substituted meso-aryl BODIPY systems bearing para-electron-with-
drawing carboxyl groups are reported in the literature. The experi-
mental spectroscopic data found for dyes 1 and 2 in aqueous
conditionsarecomparabletothoserecentlyreportedforbis-sulfonic
BODIPY dyes (kmax (abs) = 523, kmax (em) = 539 nm).1
2
Eur. J. 2009, 15, 4553–4564.
3.
(a) Forgie, J. C.; Skabara, P. J.; Stibor, I.; Vilela, F.; Vobecka, Z. Chem. Mater. 2009,
2
1, 1784–1786; (b) Donuru, V. R.; Vegesna, G. K.; Velayudham, S.; Green, S.; Liu,
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3a
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(b) Ulrich, G.; Ziessel, R.; Harriman, A. Angew. Chem., Int. Ed. 2008, 47, 1184–
For all molecules, the Stokes shifts (
agreement with those reported elsewhere for meso-aryl-substi-
Dm
= 504–625 cmꢁ1) are in
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5
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2
4
tuted BODIPY dyes. These characteristics make dyes 1 and 2 valu-
able probes not only for cellular imaging under physiological
conditions but also for the selective labeling of histidine-tagged
proteins. These studies are under investigation in our laboratories.
In summary, a convergent and highly effective method has been
developed for the preparation of symmetrical NTA-BODIPY hy-
brids. Two new water-soluble mono- and bis-NTA-BODIPY dyes
have been successfully synthesized and fully characterized. The
incorporation of NTA functionalities in the BODIPY core did not im-
pact the photophysical properties of the dyes at all. Further efforts
are currently being devoted to the development of non-symmetri-
cally substituted, water-soluble NTA-BODIPY derivatives. Con-
struction of a library of NTA as well as poly-NTA-based BODIPY
dyes is also under investigation in our laboratories.
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We acknowledge Dr. Bernard Barlaam from Astra-Zeneca (Re-
ims) for scientific discussions, and the CNRS for financial support
of MB.
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Supplementary data
2
2