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Chem. Mater.

2008, 20, 16851687

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Pyridyl-Functionalized and Water-Soluble Carbon Nano Onions: First Supramolecular Complexes of Carbon Nano Onions
Amit Palkar, Amar Kumbhar, Andreas J. Athans, and Luis Echegoyen*,
Department of Chemistry, 459 H.L. Hunter Chemistry Laboratory, Clemson UniVersity, Clemson, South Carolina 29634, and Electron Microscope Facility AdVanced Materials Research Laboratories, 91 Technology DriVe, Anderson, South Carolina 29625 ReceiVed December 12, 2007 ReVised Manuscript ReceiVed January 16, 2008

Scheme 1. Synthesis of Pyridyl CNOs (Py-CNOs)

Because of the fascinating properties of fullerenes and carbon nanotubes,2 they have been frequently used in supramolecular assemblies in an effort to obtain materials with interesting physical and electronic properties.3 However, carbon nano onions (CNOs), which are other allotropes of the carbon family and are expected to exhibit similar behavior, have never been explored for this purpose. Structurally, CNOs are the spherical analogues of multiwalled carbon nanotubes. These spherical multishelled fullerene structures were rst discovered in 1992 by Ugarte4 and can be produced by high-temperature annealing of commercially available detonation nanodiamond.5 Recently, we described several functionalization methods for the syntheses of soluble CNOs.6 The solubilization of these CNOs leads to new materials that combine the properties of the CNOs with those of the organic moieties that are attached. This offers new opportunities for potential applications in nanocomposite materials, hydrogen storage, catalysis, and separations. Here, we report a simple approach for the attachment of pyridyl ligands to the CNO surface in order to obtain water-soluble CNOs.7 These ligands can undergo complexation with transition metals such as zinc, platinum, or palladium to form higher supramolecular architectures. As an example of this, we demonstrate the binding of the pyridyl groups of CNOs via axial ligation to zinc metal in zinc tetra-phenyl porphyrin (ZnTPP), giving rise to the rst CNO-porphyrin nanohybrid.
* Corresponding author. E-mail: luis@clemson.edu. Clemson University. Electron Microscope Facility Advanced Materials Research Laboratories.

(1) (a) Echegoyen, L.; Echegoyen, L. E. Acc. Chem. Res. 1998, 31, 593 601. (b) Hirsch, A. Fullerenes Relat. Struct. 1999, 199, 165. (2) (a) Sun, Y. P.; Fu, K. F.; Lin, Y.; Huang, W. J. Acc. Chem. Res. 2002, 35, 10961104. (b) Wong, E. W.; Sheehan, P. E. Science 1997, 277 1971. (3) (a) Tashiro, K.; Aida, T. Chem. Soc. ReV. 2007, 36, 189197. (b) Bonifazi, D.; Enger, O.; Diederich, F. Chem. Soc. ReV. 2007, 36, 390 414. (c) Sgobba, V.; Rahman, G. M. A.; Guldi, D. M.; Jux, N.; Campidelli, S.; Prato, M. AdV. Mater. 2006, 18, 22642269. (4) UgarteD, Nature 1992, 359, 707709. (5) Kuznetsov, V. L.; Chuvilin, A. L.; Butenko, Y. V.; Malkov, I. Y.; Titov, V. M. Chem. Phys. Lett. 1994, 222, 343348. (6) (a) Rettenbacher, A. S.; Elliott, B.; Hudson, J. S.; Amirkhanian, A.; Echegoyen, L. Chem. Eur. J. 2005, 12, 376387. (b) Palkar, A.; Melin, F.; Cardona, C. M.; Elliott, B.; Naskar, A. K.; Kumbhar, A.; Edie, D. D.; Echegoyen, L. Chem. Asian J. 2007, 2, 625633. (7) (a) Calvert, P. Nature 1999, 399, 210. (b) Davis, M. E. Nature 2002, 417, 813. (c) Stepanow, S.; Lingenfelder, M.; Dmitriev, A.; Spillmann, H.; Delvigne, E.; Lin, N.; Deng, X. B.; Cai, C. Z.; Barth, J. V.; Kern, K. Nat. Mater. 2004, 3, 229.

The carbon nano onions were synthesized using the procedure reported earlier.6 The pyridyl functionalization was carried out as depicted in Scheme 1, where the carbon nano onions were rst oxidized using a concentrated acid mixture followed by amidation using 4-aminopyridine. The resulting product was soluble in water to the extent of 2 mg/mL. The pyridyl-functionalized CNOs (Py-CNOs) were characterized using TEM, NMR, UV/vis, Raman spectroscopy, and TGA. Figure 1 shows the TEM micrograph of Py-CNOs. Prominent features of the CNOs with concentric shells and a hollow core are clearly seen. The Py-CNOs have an average size of 6 nm, which is consistent with the size of pristine CNOs. Figure 2 shows the 1H and 13C NMR spectra of the PyCNOs. The 1H NMR spectrum shows two doublets at 6.8 and 8.0 ppm corresponding to the protons of the pyridyl group. Similar results have been obtained previously for C60 as well as the single-walled carbon nanotubes functionalized with pyridyl ligands.8 It can be clearly seen that the protons on the carbon ortho to the amide linkage are more shielded and show an upeld shift of 0.2 ppm with respect to the starting material 4-aminopyridine (see the Supporting Information). The signals from the protons of the pyridyl ring are sharp and well-dened as in the case of pyridyl functionalized C60, and unlike the behavior seen for nanotubes where they are signicantly broadened.8 This is expected as it has been observed previously with alkanethiolfunctionalized gold nanoparticles, where the broadening of the NMR signals is a function of size of the cluster.9 The 13 C spectrum shows the presence of carbons from the pyridyl ring with chemical shift values at 109, 141, and 159 ppm. The carbons appearing at 141 and 159 ppm are shifted upeld from the corresponding carbons in the free 4-aminopyridine by 4 and 7 ppm, respectively. This again indicates that the carbon attached to the nitrogen of the amide bond as well as the carbons adjacent to it are the ones most affected due to functionalization. The carbons from the CNOs are not seen
(8) (a) Langa, F.; De la Cruz, P.; Espildora, E.; Gonzalez-Cortes, A.; de la Hoz, A.; Opez-Arza, V. J. Org. Chem. 2000, 65, 86758684. (b) Alvaro, M.; Atienzar, P.; De la Cruz, P.; Delgado, J. L.; Troiani, V.; Garcia, H.; Langa, F.; Palkar, A.; Echegoyen, L. J. Am. Chem. Soc. 2006, 128, 6626. (9) Hostetler, M. J.; Wingate, J. E.; Zhong, C. J.; Harris, J. E.; Vachet, R. W.; Clark, M. R.; Londono, J. D.; Green, S. J.; Stokes, J. J.; Wignall, G. D.; Glish, G. L.; Porter, M. D.; Evans, N. D.; Murray, R. W. Langmuir 1998, 14, 17.

10.1021/cm7035508 CCC: $40.75 2008 American Chemical Society Published on Web 02/07/2008

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Figure 3. UV/vis spectrum of Py-CNOs in distilled water. Figure 1. TEM of Py-CNOs on copper grid coated with lacey carbon. Scale bar indicates 2 nm.

Figure 4. TGA of Py-CNOs in air. Figure 2. 1H and


13

C NMR spectra of Py-CNOs in D2O.

in the NMR because of the broadening associated with the large number of carbons in the outer shell of the CNOs.6 The UV/visible spectrum obtained in distilled water (Figure 3) shows a continuously increasing absorbance with a maximum at 262 nm similar to that seen for single-wall carbon nanotubes.10 The Raman spectrum of the residue (see the Supporting Information) shows the D and the G bands which are characteristic of nanotubes and CNOs. The D band appears at 1316 cm-1, whereas the G band appears at 1596 cm-1. The D band is also known as the disorder-induced band and is absent in single-graphite crystal where all carbons are in an sp2-hybridized state.6,11 Thus, the higher the number of sp3 carbons in the structure, the greater the intensity of the D band. The pristine CNOs already have a D band intensity higher than that of the G band.6 The D band intensity further increases in Py-CNOs because of the creation of more defects during the oxidation step of the synthesis. The presence of
(10) Guldi, D. M.; Marcaccio, M.; Paolucci, D.; Paolucci, F.; Tagmatarchis, N.; Tasis, D.; Vazquez, E.; Prato, M. Angew. Chem., Int. Ed. 2003, 42, 4206. (11) Tuinstra, F.; Koenig, J. L. J. Chem. Phys. 1970, 53, 1126.

D and G bands further conrms the presence of CNOs in the soluble sample. TGA analysis performed in air (Figure 4) shows the sharp defunctionalization curve of the aminopyridyl groups around 350 C, followed by decomposition of the CNOs beginning at 400 C. The mass loss is 43%, which corresponds to approximately one aminopyridyl group per 120 carbons. It is well-known that pyridyl ligands can undergo complexation with transition metals thus leading to the formation of nanoporous supramolecular assemblies. For example, in 2004, we reported the synthesis and complexation of an N-pyridylfulleropyrrolidine ligand with ZnTPP.12 In order to demonstrate the possibility of constructing such selfassembled nanoporous networks using Py-CNOs, a complexation with ZnTPP was performed where the pyridyl nitrogen underwent complexation with the central zinc atom as depicted in Figure 5. The complexation was followed by electrochemistry and NMR spectroscopy. Figure 6 shows the OSWV indicating the effect of complexation on the electrochemistry of ZnTPP. Typically, ZnTPP shows two oxidation and two reduction waves. The
(12) Tat, F. T.; Zhou, Z.; MacMahon, S.; Song, F.; Rheingold, A. L.; Echegoyen, L.; Schuster, D. I.; Wilson, S. R. J. Org. Chem. 2004, 69, 4602.

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Figure 5. Complexation of Py-CNO with Zn-TPP.

Figure 7. Titration of Py-CNOs with ZnTPP. The protons next to the pyridyl nitrogen show an upeld shift (bottom spectrum shows pure Py-CNOs with increasing ZnTPP as indicated by the arrow).

Notable is the fact that the shift is upeld as expected because of the shielding effect of the zinc metal. In conclusion, we have demonstrated straightforward methods for solublizing CNOs and constructing CNO-based supramolecular systems by complexation with metal ligands. Similar complexes are possible using metals such as platinum and palladium and may have potential applications in the eld of catalysis and hydrogen storage. Further photophysical studies are in progress in order to determine the electronic interactions between the porphyrin and the pyridyl CNOs.
Figure 6. Effect of complexation of Py-CNOs with ZnTPP on the electrochemistry of ZnTPP in DMF.

half-wave potentials observed in DMF are +0.66 V, +0.37 V, -1.99 V, and -2.3 V, respectively. Upon complexation, the reduction potentials were shifted anodically by about 170 mV and the oxidation potentials by about 60 mV. This effect is due to the complexation of the pyridyl CNOs with ZnTPP. Similar effects have been observed in the electrochemistry of pyridyl-functionalized carbon nanotubes.8 The complexation was also conrmed by performing an NMR titration of the pyridyl CNOs with ZnTPP in DMF. It can be seen in Figure 7 that the protons on the carbon next to the pyridyl nitrogen shift gradually upon addition of increasing amounts of ZnTPP.

Acknowledgment. Financial support from the National Science Foundation for A.J.A. and L.E. (CHE-0509989) is greatly appreciated. This material is based on work supported by the National Science Foundation while L.E. was working at the foundation. All opinions, ndings, conclusions, or recommendations expressed herein are those of the authors and do not necessarily reect the views of the National Science Foundation.
Supporting Information Available: Experimental details, 1H and 13C, NMR spectrum of 4-aminopyridine, COSY, and Raman spectrum of Py-CNOs. This information is available free of charge via the Internet at http://pubs.acs.org.
CM7035508

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