is related to the structure of the hydrogen bond complex and
the basicity of the anions. Among anions, F- is the most
electronegative atom and, as such, usually forms the strongest
H-bond interaction with an NH or OH groups. Of particular
interest to our work is the early studies of Crabtree and
Stranes in using a sulfonamide moiety for the recognition
of anionic species.12
Among other aromatic molecules that have found utility
in the design of chromophoric supramolecular materials,
naphthalene diimide (NDI) derivatives have attracted par-
ticular attention.13,14 NDIs are compact, highly colored, and
functionalizable materials. Considering their rich spectro-
scopic and electrochemical properties, core-substituted NDI
derivatives, in particular, are ideally suited to sensor design.13
As yet though, core-substituted NDIs have not been explored
in a receptor or sensor capacity. Here, we report the use of
core-substituted NDI chromophores for anion sensing pur-
poses through the synthesis and evaluation of a ꢀ,ꢀ′-bis-
sulfonamide-quinoxaline derivative 1 (Figure 1) and compare
its sensing ability to a model system 2 which does not contain
the sulfonamide groups.
(5) (a) Yu, J. O.; Browning, C. S.; Farrar, D. H. Chem. Commun. 2008,
1020. (b) Caltagirone, C.; Hiscock, J. R.; Hursthouse, M. B.; Light, M. E.;
Gale, P. A. Chem.sEur. J. 2008, 14, 10236. (c) Caltagirone, C.; Gale, P. A.;
Hiscock, J. R.; Brooks, S. J.; Hursthouse, M. B.; Light, M. E. Chem.
Commun. 2008, 3007. (d) Pfeffer, F. M.; Lim, K. F.; Sedgwick, K. J. Org.
Biomol. Chem. 2007, 5, 1795.
(6) (a) Chang, K. J.; Kang, B. N.; Lee, M. H.; Jeong, K. S. J. Am. Chem.
Soc. 2005, 127, 12214. (b) Kim, U. I.; Suk, J. M.; Naidu, V. R.; Jeong,
K. S. Chem.sEur. J. 2008, 14, 11406. (c) Naidu, V. R.; Kim, M. C.; Suk,
J. M.; Kim, H. J.; Lee, M.; Sim, E.; Jeong, K. S. Org. Lett. 2008, 10, 5373.
(7) (a) Suk, J. M.; Jeong, K. S. J. Am. Chem. Soc. 2008, 130, 11868.
(b) Hiscock, J. R.; Caltagirone, C.; Light, M. E.; Hursthouse, M. B.; Gale,
P. A. Org. Biomol. Chem. 2009, 7, 1781. (c) Chmielewski, M. J.; Zhao,
L. Y.; Brown, A.; Curiel, D.; Sambrook, M. R.; Thompson, A. L.; Santos,
S. M.; Felix, V.; Davis, J. J.; Beer, P. D. Chem. Commun. 2008, 3154. (d)
Piatek, P. V.; Lynch, M.; Sessler, J. L. J. Am. Chem. Soc. 2004, 126, 16073.
(e) Chmielewski, M. J.; Charon, M.; Jurczak, J. Org. Lett. 2004, 6, 3501.
(8) (a) Cho, E. J.; Ryu, B. J.; Lee, Y. J.; Nam, K. C. Org. Lett. 2005,
7, 2607. (b) Boiocchi, M.; Boca, L. D.; Esteban-Go´mez, D.; Fabbrizzi, L.;
Licchelli, M.; Monzani, E. J. Am. Chem. Soc. 2004, 126, 16507. (c) Kwon,
J. Y.; Jang, Y. J.; Kim, S. K.; Lee, K.-H.; Kim, J. S.; Yoon, J. J. Org.
Chem. 2004, 69, 5155. (d) Black, C. B.; Andrioletti, B.; Try, A. C.; Ruiperez,
C.; Sessler, J. L. J. Am. Chem. Soc. 1999, 121, 10438.
Figure 1. (a) Anion sensor structure illustrating where the anion
binds and (b) model NDI 2. (c) Sensing capability with color
changes upon addition of 3 equiv of anions to 1 in chloroform: no
-
anion, F-, H2PO4-, AcO-, Cl-, Br-, I-, HSO4 as their tetrabu-
tylammonium salts; [1] ) 3.5 × 10-6 M.
The core-substituted NDI sensor 1 was synthesized by the
condensation of the ortho-diamine functionalized disulfona-
mide 411,15 with tetrabromo-NDI 316 in dry DMF at 135 °C
(Scheme 1). Receptor 1 was obtained in 87% yield as a deep
blue solid after purification by column chromatography on
silica. The fact that monoannulation results in high yield can
be attributed to two factors; aniline amines such as 4 are
less nucleophilic than the aliphatic amines17 used in examples
where tetrasubstitution takes place.15 Once the first addition
is complete, the deactivating feature of the two amino groups
leads to a balance of the two effects that preclude further
addition. This result is important as it may allow variation
of the structure through the two remaining aryl bromide
groups.18
(9) (a) Das, A.; Ganguly, B.; Kumar, D. K.; Jose, D. A. Org. Lett. 2004,
6, 3445. (b) Miyaji, H.; Sessler, J. L. Angew. Chem., Int. Ed. 2001, 40,
154. (c) Jimenez, D.; Martinez-Manez, R.; Sancenon, F.; Soto, J. Tetra-
hedron Lett. 2002, 43, 2823. (d) Miyaji, H.; Sato, W.; Sessler, J. L. Angew.
Chem., Int. Ed. 2000, 39, 1777.
(10) (a) Lee, D. H.; Im, J. H.; Son, S. U.; Chung, Y. K.; Hong, J.-I.
J. Am. Chem. Soc. 2003, 125, 7752. (b) Sancenon, F.; Martinez-Manez,
R.; Soto, J. Angew. Chem., Int. Ed. 2002, 41, 1416. (c) Lee, D. H.; Lee,
K. H.; Hong, J.-I. Org. Lett. 2001, 3, 5.
(11) Examples of electron-acceptor chromophores for anion sensing:
(a) Nishiyabu, R.; Anzenbacher, P., Jr. J. Am. Chem. Soc. 2005, 127, 8270.
(b) Esteban-Go´mez, D.; Fabbrizzi, L.; Licchelli, M. J. Org. Chem. 2005,
70, 5717.
The result of adding 3 equiv of various anions (F-,
(12) (a) Kavallieratos, K.; Bertao, C. M.; Crabtree, R. H. J. Org. Chem.
1999, 64, 1675. (b) Starnes, S. D.; Arungundram, S.; Saunders, C. H.
Tetrahedron Lett. 2002, 43, 7785.
-
-
H2PO4 , AcO-, Cl-, Br-, I-, and HSO4 , added as their
tetrabutylammonium salts) to 1 in CHCl3 is shown in Figure
1c. Specifically, NDI 1 is a sensor selective for fluoride at
micromolar concentration. The dramatic anion-specific re-
(13) Core-substituted naphthalene bisimides have been previously
prepared and used. See: (a) Bhosale, S.; Jani, C.; Langford, S. Chem. Soc.
ReV. 2008, 37, 331. (b) Bhosale, S.; Sisson, A.; Talukdar, P.; Fu¨rstenberg,
A.; Banerj, N.; Vauthey, E.; Bollot, S.; Mareda, J.; Ro¨ger, C.; Wu¨rthner,
F.; Sakai, N.; Matile, S. Science 2006, 313, 84. (c) Wu¨rthner, F.; Ahmed,
S.; Thalacker, C.; Debaerdemaeker, T. Chem.sEur. J. 2002, 8, 4742. (d)
Thalacker, C.; Miura, A.; De Feyter, S.; De Schryver, F. C.; Wu¨rthner, F.
Org. Biomol. Chem. 2005, 3, 414. (e) Bhosale, S.; Sisson, A. L.; Sakai, N.;
(15) Cheeseman, G. W. H. J. Chem. Soc. 1962, 1171
.
(16) Gao, X.; Qiu, W.; Yang, X.; Liu, Y.; Wang, Y.; Zhang, H.; Qi, T.;
Liu, Y.; Lu, K.; Du, C.; Shuai, Z.; Yu, G.; Zhu, D. Org. Lett. 2007, 9,
3917.
Matile, S. Org. Biomol. Chem. 2006, 4, 3031
.
(14) For sensors derived from NDIs, see: (a) Gunnlaugsson, T.; Kruger,
P. E.; Lee, T. C.; Parkesh, R.; Pfeffer, F. M.; Hussey, G. M. Tetrahedron
Lett. 2003, 44, 6575. (b) Gunnlaugsson, T.; Kruger, P. E.; Jensen, P.; Pfeffer,
(17) Henderson, W. A., Jr.; Schultz, C. J. J. Org. Chem. 1962, 27, 4643.
(18) Addition of a second equivalent of 4 to 1, substituting the two
remaining bromine atoms, may increase the sensitivity of the sensor toward
fluoride. However, this was not possible despite many attempts.
F. M.; Hussey, G. M. Tetrahedron Lett. 2003, 44, 8909
.
Org. Lett., Vol. 11, No. 23, 2009
5419