G. S. Heo, B. Moon / Tetrahedron Letters 49 (2008) 5540–5543
5543
contact angle.12 [Piranha-treated glass (<6°), APTS-treated glass
Supplementary data
(50°), and fullerene anhydride 5-treated APTS-glass (71°) (Fig. S5)].
Amphiphilic fullerene derivative 10 could be easily prepared
from fullerene anhydride 5 by hydrolysis reaction (Scheme 3).
One equivalent of aqueous NaOH solution was added to a THF solu-
tion of fullerene anhydride 5. After stirring the two-phase mixture
overnight at rt and removing THF by evaporation, deionized water
was added to dissolve all precipitates. Finally, an orange-colored
clear solution of 10 was obtained.
It is well known that amphiphilic fullerene derivatives tend to
form self-assembled nanostructures in various shapes such as
spheres, vesicles, needles, rods, and tubules.13 Atomic force
microscopy (AFM) images of a drop-cast sample of 10 on mica
showed that amphiphilic fullerene 10 forms spherical aggregates
in regular sizes as shown in Figure 5. Dynamic light scattering
(DLS) measurement of the solution (5.6 Â 10À7 M) indicated that
the hydrodynamic diameter of the aggregates was 116 nm with
polydispersity index of 0.240 (Fig. 5a inset).
In conclusion, we have developed an efficient way of preparing
phthalic anhydride-functionalized fullerene via simple pyrolysis of
a di-t-butyl phthalate precursor. Because this protocol can produce
a high yield of the fullerene anhydride without using any addi-
tional reagents or solvents, the anhydride can be directly subjected
to coupling reactions without further purification, which had pre-
viously been an obstacle to the introduction of this useful func-
tional group on fullerenes. The resulting fullerene anhydride 5
exhibits good solubility in common organic solvents and high reac-
tivity with various amine-containing materials. We envision that
this methodology may also be applicable to the functionalization
of other thermally stable solid materials with anhydride groups
such as carbon nanotubes, silicates, and zeolites.
Supplementary data (experimental details and spectral charac-
terization data for 3–5 and 7–10) associated with this article can be
References and notes
1. (a) Fullerenes: Chemistry, Physics, and Technology; Kadish, K. M., Ruoff, R. S., Eds.;
Wiley-Interscience: New York, 2000; (b) Guldi, D. M.; Prato, M. . Acc. Chem. Res.
2000, 33, 695–703; (c) Mateo-Alonso, A.; Guldi, D. M.; Paolucci, F.; Prato, M. .
Angew. Chem., Int. Ed. 2007, 46, 8120–8126; (d) Nakamura, E.; Isobe, H. Acc.
Chem. Res. 2003, 36, 807–815; (e) Segura, J. L.; Martin, N.; Guldi, D. M. Chem.
Soc. Rev. 2005, 34, 31–47.
2. (a) Hirsch, A.; Brettreich, M. Fullerenes: Chemistry and Reactions; Wiley-VCH:
Weinheim, 2005; (b) Zhang, W.; Swager, T. M. J. Am. Chem. Soc. 2007, 129,
7714–7715.
3. (a) Zhang, W.-B.; Tu, Y.; Ranjan, R.; Van Horn, R. M.; Leng, S.; Wang, J.; Polce, M.
J.; Wesdemiotis, C.; Quirk, R. P.; Newkome, G. R.; Cheng, S. Z. D. Macromolecules
2008, 41, 515–517; (b) Iehl, J.; Pereira de Freitas, R.; Delavaux-Nicot, B.;
Nierengarten, J.-F. Chem. Commun. 2008, 2450–2452; (c) Iehl, J.; Pereira de
Freitas, R.; Nierengarten, J.-F. Tetrahedron Lett. 2008, 49, 4063–4066.
4. (a) Periya, V. K.; Koike, I.; Kitamura, Y.; Iwamatsu, S.-I.; Murata, S. . Tetrahedron
Lett. 2004, 45, 8311–8313; (b) Zhang, X.; Foote,C. S. J. Am. Chem. Soc. 1995, 117,
4271–4275.
5. Moon, B.; Hoye, T. R.; Macosko, C. W. Macromolecules 2001, 34, 7941–
7951.
6. Prato, M.; Maggini, M. Acc. Chem. Res. 1998, 31, 519–526.
7. (a) Maggini, M.; Scorrano, G.; Prato, M. J. Am. Chem. Soc. 1993, 115, 9798–9799;
(b) Guldi, D. M.; Maggini, M.; Scorrano, G.; Prato, M. J. Am. Chem. Soc. 1997, 119,
974–980.
8. Martin, N.; Altable, M.; Filippone, S.; Martin-Domenech, A.; Echegoyen, L.;
Cardona, C. M. Angew. Chem., Int. Ed. 2006, 45, 110–114.
9. Almost no trace of C60 fullerene was observed in the TLC analysis of the crude
pyrolysis product 5 and its purity was verified by elemental analysis (Anal.
Calcd for C73H13NO3: C, 92.11; H, 1.38; N, 1.47. Found: C, 92.06; H, 1.47; N,
1.37).
10. Bauer, J.; Rademann, J. Tetrahedron Lett. 2003, 44, 5019–5023.
11. (a) Song, T.; Dai, S.; Tam, K. C.; Lee, S. Y.; Goh, S. H. Polymer 2003, 44, 2529–
2536; (b) Dai, S.; Ravi, P.; Tan, C. H.; Tam, K. C. Langmuir 2004, 20, 8569–8575;
(c) Yu, H.; Gan, L. H.; Hu, X.; Gan, Y. Y. Polymer 2007, 48, 2312–2321.
12. (a) Chen, K.; Caldwell, W. B.; Mirkin, C. A. J. Am. Chem. Soc. 1993, 115, 1193–
1194; (b) Choi, S. Y.; Lee, Y.; Park, Y. S.; Ha, K.; Yoon, K. B. J. Am. Chem. Soc. 2000,
122, 5201–5209.
13. (a) Guldi, D. M.; Zerbetto, F.; Georgakilas, V.; Prato, M. Acc. Chem. Res. 2005, 38,
38–43; (b) Zhou, S.; Burger, C.; Chu, B.; Sawamura, M.; Nagahama, N.;
Toganoh, M.; Hackler, U. E.; Isobe, H.; Nakamura, E. Science 2001, 291, 1944–
1947.
Acknowledgments
This work was supported by the Korea Research Foundation
under grant KRF-2006-005-J02101 and by the Center for Bioactive
Molecular Hybrid (CBMH) of KOSEF. G.S.H. gratefully acknowledges
a fellowship of the BK21 program from the Ministry of Education
and Human Resources Development.