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Wavelength (nm)
Figure 3. UV–vis spectra obtained by addition of PPi (400
l
M) to an ensemble
solution of [CuL2ꢁPV] (20
lM) in 80/20 (v/v) MeCN/H2O solution buffered with
10 mM HEPES at pH 6.4.
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through one Cu2+ ion, which was similar to the binding mode of PPi
with the dinuclear DPA–2Zn2+ derivatives reported by Yoon and
co-workers24 and Hong and co-workers.5b
Similar experiments have been run with the mononuclear CuL1
complex. The results showed that in the presence of any anions in
an ensemble solution of [CuL1ꢁPV] the yellow solution of the un-
bound dye was not observed (Fig. S8, Supplementary data). This re-
sult strongly supports the fact that the cooperative action of two
Cu2+ ions in solution is required for selective sensing of PPi.
In conclusion, we have successfully synthesized mono- and
dinuclear Cu(II) complexes of calix[4]arene containing a tripodal
amine, CuL1 and CuL2. CuL2 was demonstrated to be a remarkable
IDA receptor for PPi. A rationale to account for the selectivity of
CuL2 toward PPi requires matching of the distance between the
donor atoms of PPi with the Cu2+–Cu2+ distance in the CuL2 cavity.
In addition, the preorganization of calix[4]arene in the cone confor-
mation and steric hindrance between the two bulky tripodal amine
parts are the most important factors controlling the Cu2+–Cu2+ dis-
tance. This resulted in selective recognition of CuL2 toward PPi
over other anions. Further studies are underway in our laboratory
to prepare anion selective electrodes from CuL2.
11. Groenen, L. C.; Ruël, B. H. M.; Casnati, A.; Verboom, W.; Pochini, A.; Ungaro, R.;
Reinhoudt, D. N. Tetrahedron 1991, 47, 8379–8384.
12. Navakun, K.; Tuntulani, T.; Ruangpornvisuti, V. J. Inclusion Phenom. 2000, 38,
113–122.
13. Burdette, S. C.; Frederickson, C. J.; Bu, W.; Lippard, S. J. J. Am. Chem. Soc. 2003,
125, 1778–1787.
14. Ionophore L1, 1H NMR (400 MHz, CDCl3, ppm): d 10.20 (s, 1H, –OH), 9.49 (s, 2H,
–OH), 8.44 (d, 2H, J = 4.0 Hz, ArH), 7.49 (t, 2H, J = 6.0 Hz, ArH), 7.37 (d, 2H,
J = 4.0 Hz, ArH), 7.34 (d, 2H, J = 8.0 Hz, ArH), 7.13 (s, 2H, ArH), 7.12 (s, 1H, ArH),
7.07 (d, 2H, J = 2.0 Hz, ArH), 7.05 (s, 2H, ArH), 7.03 (s, 2H, ArH), 7.02 (s, 2H, ArH),
6.94 (m, 2H, ArH), 8.82 (s, 1H, –NH–), 6.54 (t, 1H, J = 7.6 Hz, ArH), 6.40 (d, 1H,
J = 8.0 Hz, ArH), 4.70 (d, 2H, J = 3.2 Hz, –CH2–NH–), 4.64 (s, 4H, –O–CH2–O–),
4.53 (d, 2H, J = 12.8 Hz, Ar–CH2–Ar), 4.24 (d, 2H, J = 13.6 Hz, Ar–CH2–Ar), 3.83
(s, 4H, –CH2–N), 3.69 (s, 2H, –CH2–N), 3.41 (dd, 4H, J = 7.6 Hz, J = 12.8, 13.6 Hz,
Ar–CH2–Ar), 1.23 (s, 36H, p-tert-butyl); 13C NMR (100 MHz, CDCl3, ppm): d
159.24, 156.11, 149.12, 149.04, 148.39, 148.29, 148.09, 147.85, 143.50, 143.12,
136.30, 133.61, 130.94, 128.74, 128.53, 128.12, 128.07, 127.75, 127.69, 126.56,
125.82, 125.71, 125.66, 123.18, 121.90, 121.51, 121.10, 115.32, 110.80, 110.20,
74.78, 60.13, 58.47, 41.73, 34.26, 33.99, 33.93, 33.00, 32.18, 31.50, 31.25;
HRMS-ESI: [M+H]+ calcd for C72H84N4O5, 1085.6670: found 1085.6671.
15. Ionophore L2, 1H NMR (400 MHz, CDCl3): d 8.42 (d, 4H, J = 4.0 Hz, ArH), 7.65 (d,
2H, J = 2.4 Hz, ArH), 7.46 (m, 4H, ArH), 7.35 (d, J = 7.6 Hz, 2H, ArH), 7.30 (s, 4H,
ArH), 7.19 (m, 2H, ArH), 7.06 (m, 8H, ArH), 7.05 (m, 2H, ArH), 6.95 (d, 4H,
J = 8.4 Hz, ArH), 6.89 (s, 4H, ArH) 6.86 (d, 2H, J = 7.2 Hz, ArH), 6.72 (s, 2H, –NH–),
6.54 (m, 2H, ArH), 6.44 (d, 2H, J = 8.0 Hz, ArH), 4.53 (d, 4H, J = 4.8 Hz, –CH2–
NH–), 4.44 (d, 4H, J = 12.8 Hz, Ar–CH2–Ar), 4.35 (s, 8H, –CH2–O–), 3.80 (s, 8H, –
CH2–N), 3.68 (s, 4H, –CH2–N), 3.33 (d, 4H, J = 13.2 Hz, Ar–CH2–Ar), 1.26 (s, 18H,
p-tert-butyl), 1.03 (s, 18H, p-tert-butyl); 13C NMR (100 MHz, CDCl3, ppm): d
159.23, 156.24, 150.35, 149.73, 149.07, 148.21, 147.34, 141.69, 136.29, 133.12,
130.97, 128.77, 128.56, 128.52, 127.93, 127.63, 125.72, 125.20, 123.20, 121.91,
121.55, 120.71, 115.35, 110.78, 110.32, 74.16, 66.65, 60.16, 58.47, 41.76, 34.04,
33.84, 31.83, 31.66, 31.10; HRMS-ESI: [M+H]+ calcd for C100H112N8O6,
1521.8705: found 1521.8715.
Acknowledgments
Financial support from The Thailand Research Fund
(MRG5380064 and RTA5080006), a Grant from the Faculty of Sci-
ence, Burapha University, and Center for Innovation in Chemistry
(PERCH-CIC) and Commission on Higher Education, Ministry of
Education, are gratefully acknowledged.
Supplementary data
Supplementary data (additional 1H and 13C NMR spectra of L1
and L2, and displacement results of CuL1 with various anions are
available) associated with this article can be found, in the online
ˇ
16. Frkanec, L.; Višnjevac, A.; Kojic´-Prodic´, B.; Zinic´, M. Chem. Eur. J. 2000, 6, 442–
453.
17. CuL1; A methanolic solution of CuCl2ꢁ2H2O (24 mg, 0.14 mmol) in 5 mL CH3OH
was added to a suspension of L1 (0.108 g, 0.09 mmol) in methanol giving a
deep-green solution. The solution was allowed to stand at room temperature.
After 1 week, green block-shaped X-ray diffraction quality single crystals of
CuL1 were obtained (80 mg, 73%). HRMS-ESI: [M+Cl]+ calcd for
C72H84ClCuN4O5, 1182.5426: found 1182.5424.
18. CuL2: A methanolic solution of CuCl2ꢁ2H2O (26 mg, 0.15 mmol) was added to a
methanolic suspension of ionophore L2 (110.9 mg, 0.06 mmol); the color of the
solution changed to deep-green immediately. After standing the green solution
at room temperature for 1 week, the deep-green solid appeared. This was
filtered and washed with MeOH to give CuL2 in 42% yield (111 mg). HRMS-ESI:
[M+Cl]+ calcd for C100H112Cl3Cu2N8O6, 1751.6362: found 1751.6365.
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