ability of structures related to 1, possessing more water soluble
functional groups, in greater detail.
(g) D. Esteban-Gomez, L. Fabbrizzi and M. Liechelli, J. Org. Chem.,
2005, 70, 5717; (h) M. Tomasulo and F. M. Raymo, Org. Lett., 2005, 7,
4633.
6 (a) J. Massue, S. J. Quinn and T. Gunnlaugsson, J. Am. Chem. Soc.,
2008, 130(22), 6900–6901; (b) S. E. Plush and T. Gunnlaugsson, Org.
Lett., 2007, 9, 1919; (c) H. N. Lee, K. M. K. Swamy, S. K. Kim, J.-Y.
Kwon, Y. Kim, S.-J. Kim, Y.-J. Yoon and Y. Yoon, Org. Lett., 2007, 9,
243; (d) J. P. Leonard, C. M. G. dos Santos, S. E. Plush, T. McCabe and
T. Gunnlaugsson, Chem. Commun., 2007, 129; (e) E. J. O’Neil and B. D.
Smith, Coord. Chem. Rev., 2006, 250, 3068; (f) B. T. Nguyen and E. V.
Anslyn, Coord. Chem. Rev., 2006, 250, 3118; (g) A. J. Harte, P. Jensen,
S. E. Plush, P. E. Kruger and T. Gunnlaugsson, Inorg. Chem., 2006, 45,
9465; (h) T. Gunnlaugsson and J. P. Leonard, Chem. Commun., 2005,
3114.
7 (a) G. W. Bates, P. A. Gale and M. E. Light, Chem. Commun., 2007,
2121; (b) L. S. Evans, P. A. Gale, M. E. Light and R. Quesada, Chem.
Commun., 2006, 965.
8 K. Kavallieratos, S. R. de Gala, D. J. Austin and R. H. Crabtree, J. Am.
Chem. Soc., 1997, 119, 2325.
9 L.-H. Wei, Y.-B. He, J.-L. Wu, L.-Z. Meng and X. Yang, Supramol.
Chem., 2004, 16, 561.
10 (a) W.-X. Liu and Y.-B. Jiang, Org. Biomol. Chem., 2007, 5, 1771; (b) E.
Quinlan, S. E. Matthews and T. Gunnlaugsson, J. Org. Chem., 2007, 72,
7497; (c) E. Quinlan, S. E. Matthews and T. Gunnlaugsson, Tetrahedron
Lett., 2006, 47, 9333.
11 (a) H. D. P. Ali, P. E. Kruger and T. Gunnlaugsson, New J. Chem.,
2008, 32, 1153–1161; (b) T. Gunnlaugsson, P. E. Kruger, P. Jensen, J.
Tierney, H. D. P. Ali and G. M. Hussey, J. Org. Chem., 2005, 70, 10875.
12 (a) F. M. Pfeffer, P. E. Kruger and T. Gunnlaugsson, Org. Biomol.
Chem., 2007, 5, 1894; (b) F. M. Pfeffer, T. Gunnlaugsson, P. Jensen and
P. E. Kruger, Org. Lett., 2005, 7, 5357.
13 Other recent examples include: (a) K. M. K. Swamy, S. K. Kwon, H.
N. Lee, S. M. S. Kumar, J. S. Kim and J. Yoon, Tetrahedron Lett., 2007,
48, 8683; (b) Z. Xu, S. Kim, H. N. Kim, S. J. Han, C. Lee, J. S. Kim,
X. Qian and J. Yoon, Tetrahedron Lett., 2007, 48, 9151; (c) H. Wang
and W.-H. Chan, Org. Biomol. Chem., 2008, 6, 162; (d) K. S. Moon, N.
Singh, G. W. Lee and D. O. Jang, Tetrahedron, 2007, 63, 9106; (e) H.
M. Chawla and S. P. Singh, Tetrahedron, 2008, 64, 741; (f) M. Kumar, J.
N. Babu, V. Bhalla and N. S. Athwal, Supramol. Chem., 2007, 19, 511;
(g) D. Saravankumar, S. Deveraj, S. Iyyampillai, K. Mohandoss and
M. Kandaswamy, Tetrahedron Lett., 2008, 49, 127; (h) C. Liu, X. Qian,
J. Wang and Z. Li, Tetrahedron Lett., 2008, 49, 1087; (i) R. Nishiyabu
and P. Anzenbacher, Jr., J. Am. Chem. Soc., 2005, 127, 8270.
14 (a) C. Perez-Casas and A. K. Yatsimirsky, J. Org. Chem., 2008, 73,
2275; (b) T. Gunnlaugsson, P. E. Kruger, T. C. Lee, R. Parkesh, F.
M. Pfeffer and G. M. Hussey, Tetrahedron Lett., 2003, 44, 6575; (c) T.
Gunnlaugsson, P. E. Kruger, P. Jensen, F. M. Pfeffer and G. M. Hussey,
Tetrahedron Lett., 2003, 44, 8909; (d) S. Camiolo, P. A. Gale, M. B.
Hursthouse and M. E. Light, Org. Biomol. Chem., 2003, 1, 741; (e) D.
E. Go´mez, L. Fabbrizzi, M. Licchelli and E. Monzani, Org. Biomol.
Chem., 2005, 3, 1495.
Acknowledgements
We would also like to thank the SFI, CSCB and Trinity College
Dublin for financial support. We would like to thank Dr Dilip Rai,
CSCB, UCD for MS analysis and Dr Brendan Twamley for his
help with resolving the X-ray structure of 1.
Notes and references
§ Synthesis of 1,6-bis-[4-nitrophenyl(thioureidocarbamoyl)]-pyridine (1).
2,6-Pyridinedicarboxylic acid, dihydrazide (0.281 g, 1.03 mmol, 1 eq) and
4-nitrophenylisothiocyanate (0.518 g, 2.88 mmol, 2 eq) were refluxed in
acetonitrile for 16 h. The precipitate was isolated by suction filtration and
washed with acetonitrile to give a pale yellow solid, 0.784 g, 98%. Mp 203–
205 ◦C; dH (600 MHz, DMSO-d6): 11.30 (2H, br s, NHNHurea), 10.37 (2H,
br s, NHNHurea), 10.20 (2H, br s, NHurea), 8.31 (2H, br s, CHpy), 8.30 (1H,
br s, CHpy), 8.22 (4H, br s, CHCNO2), 7.92 (4H, br s, Hz, CHCNH,);
dC (150 MHz DMSO-d6) 181.1 (C S), 162.8 (C O), 147.8 (C6), 145.7
(CNH), 143.6 (CNO2), 139.8 (C3/5), 125.6 (C4), 125.2 (CHCNH), 123.9
(CHCNO2); dN (600 MHz DMSO-d6) 129.6 (Namido), 127.7 (NHurea), 126.2
(NHNH); IR nmax (cm-1) 3128, 2962, 1704, 1597, 1549, 1506, 1469, 1345,
1278, 1219, 1157, 1002, 887, 851, 745, 698. HRMS (ES+): calculated for
C21H18N9O6S2: 556.0821, found: 556.0822 (M + H).
=
=
¶ X-Ray crystallographic information. The data were collected on a Rigaku
Saturn 724 CCD diffractomer. A crystal, of dimensions 0.27 ¥ 0.20 ¥
0.08 mm, was selected and mounted on a 0.30 mm quartz fibre tip
and immediately placed on the goniometer head in a 123 K N2 gas
stream. The data set was collected using Crystalclear-SM 1.4.0 software
and 1680 diffraction images of 0.5◦ per image were recorded. Data
integration, reduction, corrections for absorption and polarization effects
were all performed using Crystalclear-SM 1.4.0 software. Space group
determination, structure solution and refinement were obtained using
Crystalstructure ver. 3.8 and Shelxtl19 ver. 6.14 software. Crystal data:
C27H35N9O9S5, M = 789.99, ◦triclinic, a = 14.4◦89(3), b = 15.929◦(5), c =
˚
17.154(5) A, a = 87.377(7) , b = 68.142(6) , g = 81.774(8) , U =
3
¯
˚
3636.5(17) A , T = 123 K, space group P1, Z = 4, m (Mo-Ka) =
0.381 mm-1, 36 636 reflections collected, 12 589 unique, (Rint = 0.0430),
R = 0.0815, wR2 [I > 2s(I)] = 0.2394. CCDC deposition number 649247.
1 J. L. Sessler, P. A. Gale and W. S. Cho, Anion Receptor Chemistry, Royal
Society of Chemistry, Cambridge, UK, 2006.
2 T. Gunnlaugsson, M. Glynn, G. M. Tocci (ne´e Hussey), P. E. Kruger
and F. M. Pfeffer, Coord. Chem. Rev., 2006, 250, 3094.
3 (a) P. A. Gale, Acc. Chem. Res., 2006, 39, 465; (b) P. A. Gale and
R. Quesada, Coord. Chem. Rev., 2006, 250, 3219; (c) P. Padros and
R. Quesada, Supramol. Chem., 2008, 20, 201; (d) J. W. Steed, Chem.
Commun., 2006, 2637; (e) E. A. Katayev, Y. A. Ustynyuk and J. L.
Sessler, Coord. Chem. Rev., 2006, 250, 3004; (f) S. O. Kang, Md. A.
Hossain and K. Bowman-James, Coord. Chem. Rev., 2006, 250, 3038;
(g) T. Gunnlaugsson, H. D. P. Ali, M. Glynn, P. E. Kruger, G. M.
Hussey, F. M. Pfeffer, C. M. G. dos Santos and J. Tierney, J. Fluoresc.,
2005, 15, 287; (h) R. Mart´ınez-Ma´n˜ez and F. Sanceno´n, Chem. Rev.,
2003, 103, 4419.
4 (a) C. M. G. dos Santos and T. Gunnlaugsson, Tetrahedron Lett., 2007,
48, 3135; (b) R. M. Duke and T. Gunnlaugsson, Tetrahedron, 2007, 48,
8043; (c) A. P. Davis, J. E. O’Brien and M. Glynn, Org. Biomol. Chem.,
2005, 3, 48; (d) T. Gunnlaugsson, A. P. Davis, J. E. O’Brien and M.
Glynn, Org. Lett., 2002, 4, 2449; (e) T. Gunnlaugsson, A. P. Davis and
M. Glynn, Chem. Commun., 2001, 2556.
5 (a) A. J. Lowe, G. A. Dyson and F. M. Pfeffer, Eur. J. Org. Chem.,
2008, 1559; (b) F. M. Pfeffer, M. Seter, N. Lewcenko and N. W. Barnett,
Tetrahedron Lett., 2006, 47, 5251; (c) P. D. Beer, M. R. Sambrook and
D. Curiel, Chem. Commun., 2006, 2105; (d) F. Y. Wu, Z. Li, L. Guo,
X. Wang, M. H. Lin, Y. F. Zhao and Y. B. Jiang, Org. Biomol. Chem.,
2006, 4, 624; (e) K. Ghosh and S. Adhikari, Tetrahedron Lett., 2006, 47,
8165; (f) Y. Li, L. F. Cao and H. J. Tian, J. Org. Chem., 2006, 71, 8279;
15 Due to lack of solubility of 1 in pure H2O, we had to use the mixed
solvent system. We are currently working on other derivatives of 1 with
the aim of obtaining fully H2O soluble sensors.
16 Due to the presence of H2O in solution, these titrations required
higher concentrations of anion in order for the plateau to be reached.
-
Titrations of 1 using H2PO4 and pyrophosphate were also carried out
at two different concentrations: 1 ¥ 10-5 M and 3 ¥ 10-5 M, respectively.
The changes in the absorption spectra of 1 were identical. Nevertheless,
no significant changes were seen in the absorption spectra until after
the addition of one and two equivalents of these anions, respectively.
We believe that this is possibly due to complexed kinetics, or that some
aggregation phenomenon is initially occurring. We are currently in the
process of elucidating this phenomenon.
17 It is also worth pointing out that the ratio between the absorption
maxima at 344 and 412 nm, respectively (Fig. 3), is less than that
observed in pure DMSO solution (Fig. 2).
18 (a) T. Gunnlaugsson, A. P. Davis, J. E. O’Brien and M. Glynn, Org.
Biomol. Chem., 2005, 3, 48; (b) T. Gunnlaugsson, A. P. Davis, G. M.
Hussey, J. Tierney and M. Glynn, Org. Biomol. Chem., 2004, 2, 1856.
19 SMART Software Reference Manual, version 5.625, Bruker Analytical
X-Ray Systems Inc., Madison, WI, 2001, G. M. Sheldrick, SHELXTL.
4092 | Org. Biomol. Chem., 2008, 6, 4089–4092
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