CH2Cl2–MeOH (40 : 1) as the eluants, to give 1 as a white
1
powder (21 mg, 30%): mp 226–227 uC; H NMR (400 MHz,
CDCl3): d =3.07 (s, 6H), 6.72 (dd, J = 8.7, 2.4 Hz, 1 H), 7.29
(d, J = 2.6 Hz, 1 H), 7.52 (d, J = 8.7 Hz, 1 H); 13C NMR (400
MHz, CDCl3): d = 40.1, 101.8, 109.0, 112.3, 120.6, 123.0,
135.1, 152.0; ESI-MS: 191.2 (M+); HRMS (ESI): calcd for
(C9H11BN2O2?2NBA?2H2O): 460.1554; found: 460.1577.
Acknowledgements
The present research was financially supported by NSFC,
Chinese Academy of Sciences and State Key Basic Research
Program (2006CB806200). D. Zhang thanks the National
Science Fund for Distinguished Young Scholars. The authors
thank Professor H. Hu for his kind help on crystal structure
refinement.
Fig. 7 Fluorescence spectra of 2 (5.0 6 1025 M) in the presence of
different amounts of F2 in DMF; lex = 295 nm.
References
Summary
1 (a) E. Lippert, W. Lu¨der, F. Moll, H. Nagele, H. Boos, H. Prigge
and I. Siebold-Blankenstein, Angew. Chem., 1961, 73, 695–706; (b)
W. Rettig, Angew. Chem., Int. Ed. Engl., 1986, 25, 971–988 and
references therein.
2 (a) K. Rotkiewicz, K. H. Grellmann and Z. R. Grabowski, Chem.
Phys. Lett., 1973, 19, 315–318; (b) W. Rettig, M. Maus, in
Conformational Analysis of Molecules in Excited States, ed.
J. Waluk, Wiley-VCH, New York, 2000, ch. 1, pp. 1–55; (c)
Z. R. Grabowski, K. Rotkiewicz and W. Rettig, Chem. Rev., 2003,
103, 3899–4032 and references therein.
By coupling the features of DMABN and boronic acid (and
boronate), compounds 1 and 2 were designed and synthesized
for sensing saccharides and F2. Fluorescent spectral changes
were observed for 1 after reaction with fructose, galactose,
mannose and glucose, and the corresponding binding con-
stants were estimated. The results show that compound 1 can
bind fructose more strongly than other saccharides tested.
Interestingly, both absorption and fluorescence spectral
changes occurred for compound 2 after addition of F2, but
not with Cl2, Br2 or I2. These results indicate that compound
2 is a potentially selective sensor for F2.
3 (a) W. Rettig, B. Bliss and K. Dirnberger, Chem. Phys. Lett., 1999,
305, 8–14; (b) W. Rettig and B. Zietz, Chem. Phys. Lett., 2000, 317,
187–196; (c) W. Rettig and S. Lutze, Chem. Phys. Lett., 2001, 341,
263–271; (d) J. Dobkowski, J. Wo´jcik, W. Kozminski, R. Kolos,
J. Waluk and J. Michl, J. Am. Chem. Soc., 2002, 124, 2406–2407;
(e) D. Rappoport and F. Furche, J. Am. Chem. Soc., 2004, 126,
1277–1284; (f) C. Jamorski Jodicke and H. P. Luthi, J. Am. Chem.
Soc., 2003, 125, 252–264; (g) B. Mennucci, A. Toniolo and
J. Tomasi, J. Am. Chem. Soc., 2000, 122, 10621–10630; (h)
W. Schuddeboom, S. A. Jonker, J. M. Warman, U. Leinhos,
W. Ku¨hnle and K. A. Zachariasse, J. Phys. Chem., 1992, 96,
10809–10819; (i) Y. V. Il’ichev, W. Ku¨hnle and K. A. Zachariasse,
J. Phys. Chem. A, 1998, 102, 5670–5680; (j) F. Y. Wu, Z. Li,
Z. C. Wen, N. Zhou, Y. F. Zhao and Y. B. Jiang, Org. Lett., 2002,
4, 3203; (k) Z. C. Wen and Y. B. Jiang, Tetrahedron, 2004, 60,
11109.
4 (a) J. H. Hartley, T. D. James and C. J. Ward, J. Chem. Soc.,
Perkin Trans. 1, 2000, 3155–3184; (b) S. L. Wiskur, J. J. Lavigne,
H. Ait-Haddou, V. Lynch, Y. H. Chiu, J. W. Canary and
E. V. Anslyn, Org. Lett., 2001, 3, 1311–1314; (c) J. Yoon and
A. W. Czarnik, J. Am. Chem. Soc., 1992, 114, 5874–5875.
5 (a) T. D. James, K. R. A. Samankumara Sandanayake and
S. Shinkai, Angew. Chem., Int. Ed. Engl., 1996, 35, 1910–1922; (b)
K. R. A. Samankumara Sandanayake, T. D. James and S. Shinkai,
Pure Appl. Chem., 1996, 68, 1207–1212; (c) A. P. Davis and
R. S. Wareham, Angew. Chem., Int. Ed., 1999, 38, 2978–2996; (d)
H. Cao and M. D. Heagy, J. Fluoresc., 2004, 14, 569–584; (e)
T. D. James, P. Linnane and S. Shinkai, Chem. Commun., 1996,
281–287; (f) J. Yan, H. Fang and B. Wang, Med. Res. Rev., 2005,
25, 490–520 and further references therein.
Experimental
General
Melting points were measured with an XT4-100X microscope
apparatus and are uncorrected. 1H and 13C NMR spectra were
recorded on BRUCK300 MHz and BRUCK400 MHz
instruments. EI-MS was determined with AEI-MS 50. ESI-
MS spectra were determined with LCMS-2010 instruments.
Fluorescence spectra were recorded on a JASCO FP6000
spectrofluorometer in a 1-cm quartz cell. Absorption spectra
were recorded on JASCO V-570 UV/VIS/NIR spectrometer.
Column chromatography was performed with silica gel (200–
300 mesh). THF was distilled from Na and benzophenone
before use.
Compound 2 was prepared according to the reported
procedure as a white solid (yield 66%).11 Single crystals of 2
were obtained by recrystallization from CH2Cl2–cyclohexane.{
Compound 1
6 (a) E. Nakata, T. Nagase, S. Shinkai and I. Hamachi, J. Am.
Chem. Soc., 2004, 126, 490–495; (b) A. Sugasaki, K. Sugiyasu,
M. Ikeda, M. Takeuchi and S. Shinkai, J. Am. Chem. Soc.,
2001, 123, 10239–10244; (c) T. D. James, K. R. A.
Samankumara Sandanayake and S. Shinkai, Nature, 1995, 374,
345–347; (d) T. D. James, H. Shinmori and S. Shinkai, Chem.
Commun., 1997, 71–72; (e) K. Tsukagoshi and S. Shinkai, J. Org.
Chem., 1991, 56, 4089–4091; (f) T. D. James, K. R. A.
Samankumara Sandanayake and S. Shinkai, J. Chem. Soc.,
Chem. Commun., 1994, 477–478.
To the solution of compound 2 (100 mg, 1.2 mmol) in acetone–
water (9 : 1) (3 ml) a drop of 12 M HCl was added, and the
mixture solution was stirred at room temperature for 4 h. After
evaporation of solvent, the mixture was dissolved in CH2Cl2
(10 ml), followed by washing with 5% NaHCO3 (2 6 5 ml).
Then, the organic solution was dried over Na2SO4. The
crude product was purified on a silica gel column with
This journal is ß The Royal Society of Chemistry 2007
J. Mater. Chem., 2007, 17, 1964–1968 | 1967