University of Groningen Clay-fulleropyrrolidine nanocomposites Gournis, D; Jankovic, L; Maccallini, E; Benne, D; Rudolf, P; Colomer, JF; Sooambar, C; Georgakilas, [No Value]; Prato, M; Fanti, M Published in: Journal of the American Chemical Society DOI: 10.1021/ja0579661 IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below. Document Version Publisher's PDF, also known as Version of record Publication date: 2006 Link to publication in University of Groningen/UMCG research database Citation for published version (APA): Gournis, D., Jankovic, L., Maccallini, E., Benne, D., Rudolf, P., Colomer, JF., Sooambar, C., Georgakilas, N. V., Prato, M., Fanti, M., Zerbetto, F., Sarova, GH., Guldi, DM., Jankovič, L., Colomer, J-F., Georgakilas, V., Sarova, G. H., & Guldi, D. M. (2006). Clay-fulleropyrrolidine nanocomposites. 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For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Download date: 05-10-2021 Published on Web 04/18/2006 Clay-Fulleropyrrolidine Nanocomposites Dimitrios Gournis,*,†,‡ Lubosˇ Jankovicˇ,† Enrico Maccallini,‡ Darja Benne,‡ Petra Rudolf,*,‡ Jean-Franc¸ois Colomer,§ Chloe´ Sooambar,| Vasilios Georgakilas,# Maurizio Prato,*,| Marianna Fanti,£ Francesco Zerbetto,*,£ Ginka H. Sarova,+ and Dirk M. Guldi*,+ Contribution from the Department of Materials Science and Engineering, UniVersity of Ioannina, GR-45110 Ioannina, Greece, Materials Science Centre, UniVersity of Groningen, Nijenborgh 4, NL-9747 AG Groningen, The Netherlands, Laboratoire de Re´sonance Magne´tique Nucle´aire, Faculte´s UniVersitaires Notre-Dame de la Paix, 61 rue de Bruxelles, B-5000 Namur, Belgium, Dipartimento di Scienze Farmaceutiche, UniVersita` di Trieste, Piazzale Europa 1, I-34127 Trieste, Italy, Institute of Materials Science, NCSR “DEMOKRITOS”, Ag. ParaskeVi-Attikis, GR-15310 Athens, Greece, Dipartimento di Chimica “G. Ciamician”, UniVersita` di Bologna, V. F. Selmi 2, I-40126 Bologna, Italy, and Institute for Physical Chemistry, Friedrich-Alexander-UniVersita¨t Erlangen-Nu¨rnberg, Egerlandstr. 3, D-91058 Erlangen, Germany Received November 23, 2005; E-mail: [email protected]; [email protected]; [email protected]; [email protected]; [email protected] Abstract: In this work, we describe the insertion of a water-soluble bisadduct fulleropyrrolidine derivative into the interlayer space of three layered smectite clays. The composites were characterized by a combination of powder X-ray diffraction, transmission electron microscopy, X-ray photoemission and FTIR spectroscopies, and laser flash photolysis measurements. The experiments, complemented by computer simulations, give insight into the formation process, structural details, and properties of the fullerene/clay nanocomposites. The reported composite materials constitute a new hybrid system, where C60 differs from its crystals or its solutions, and open new perspectives for the design and construction of novel C60-based organic/clay hybrid materials. Introduction “storage” that gives unique properties to clay minerals, which Smectite clays are a class of layered aluminosilicate minerals can be used as catalysts,3 templates4 in organic synthesis, or as - with a unique combination of swelling, intercalation, and ion building stones for composite materials.5 7 The nature of the exchange properties that make them valuable nanostructures in microenvironment between the aluminosilicate sheets regulates diverse fields.1,2 Their structure consists of an octahedral alumina the topology of the intercalated molecules and affects possible layer fused between two tetrahedral silica layers. Smectite clays supramolecular rearrangements or reactions, such as self- have a cation exchange capacity, which depends on the assembling processes that are usually not easily controlled in - substitution of low-valent atoms, such as Mg2+ for Al3+ in the the solution phase.5 7 octahedral sheet, and Al3+ for Si4+ in the tetrahedral sites. As Fullerenes have been extensively studied during the past a consequence, the layers are negatively charged and neutrality decade.8 Their physical and chemical properties have been is obtained, for example, by hydrated cations present in the scrutinized, and a high number of organic derivatives and galleries. The intercalation process in these systems is equivalent composites have been prepared and characterized. Drawbacks to ion exchange and, unlike for intercalation compounds of (3) (a) Ballantine, J. A. NATO-ASI Ser. C 1986, 165, 197. (b) Cornelis, A.; graphite, it does not involve necessarily charge transfer between Laszlo, P. NATO-ASI Ser. C 1986, 165, 213. (4) (a) Georgakilas, V.; Gournis, D.; Petridis, D. Angew. Chem., Int. Ed. 2001, the guest and host species. These materials have the natural 40, 4286. (b) Georgakilas, V.; Gournis, D.; Bourlinos, A. B.; Karakassides, ability to adsorb organic or inorganic guest cationic species (and M. A.; Petridis, D. Chem.sEur. J. 2003, 9, 3904. (5) Theng, B. K. G. The Chemistry of Clay Organic Reactions; Adam Hilger: even neutral molecules) from solutions, and it is this cation London, 1974. (6) (a) Kloprogge, J. T. J. Porous Mater. 1998, 5, 5. (b) Gil, A.; Gandia, L. † University of Ioannina. M.; Vicente, M. A. Catal. ReV. Sci. Eng. 2000, 42, 145. (c) Ma, Y.; Tong, ‡ University of Groningen. W.; Zhou, H.; Suib, S. L. Microporous Mesoporous Mater. 2000, 37, 243. § Faculte´s Universitaires Notre-Dame de la Paix. (d) Ohtsuka, K. Chem. Mater. 1997, 9, 2039. | Universita` di Trieste. (7) Shichi, T.; Takagi, K. J. Photochem. Photobiol. C 2000, 1, 113. # (8) (a) Prato, M.; Martin, N. J. Mater. Chem. 2002, 12, 1931. (b) Prassides, NCSR “DEMOKRITOS”. K. Physics and Chemistry of the Fullerenes; Kluwer Academic: Dordrecht, £ Universita` di Bologna. The Netherlands, 1994. (c) Kroto, H. W. The Fullerenes: New Horizons + Friedrich-Alexander-Universita¨t Erlangen-Nu¨rnberg. for the Chemistry, Physics and Astrophysics of Carbon; Cambridge (1) (a) Pinnavaia, T. J. Science 1983, 220, 365. (b) Konta, J. Appl. Clay Sci. University Press: Cambridge, 1997. (d) Hirsch, A. Fullerenes and Related 1995, 10, 275. (c) Lagaly, G. Solid State Ionics 1986, 22, 43. Structures; Springer: Berlin, 1999. (e) Kadish, K. M.; Ruoff, R. S. (2) Newman, A. C. D. Chemistry of Clays and Clay Minerals; Mineralogical Fullerenes: Chemistry, Physics and Technology; Wiley-Interscience: New Society Monograph, No. 6; Longman: London, 1987. York, 2000. (f) Diederich, F.; Thilgen, C. Science 1996, 271, 317. 6154 9 J. AM. CHEM. SOC. 2006, 128, 6154-6163 10.1021/ja0579661 CCC: $33.50 © 2006 American Chemical Society Clay−Fulleropyrrolidine Nanocomposites ARTICLES for their use in several applications, especially in those based applications. One would expect that the combined action of clay on optical and electronic properties, arise from difficulties in and fullerene derivatives in polymer matrices could provide processibility and incorporation into various solid matrices, such novel functionalities to the resulting composite materials. In as polymers, glasses, metals, and other materials, since the low particular, the inherent electronic properties of C60 as a solubility of fullerenes in different solvents is a serious obstacle. component of polymer composites could produce materials with Organic derivatization of fullerenes can help solubilization both enhanced static dissipation, better electromagnetic compatibility, in organic solvents and in water and also influence their and improved thermal conductivity. 9 properties. The chemical functionalization of the fullerene The incorporation of pure C60 into porous materials, such as sphere produces a large number of different derivatives that molecular sieves15,16 and layered double hydroxides (LDH),17-19 15 combine the desirable properties of C60 with the solubilizing has been extensively studied. Keizer et al. reported the trapping power of the side chains. One of the most versatile addition of C60 in 13 Å molecular sieves through gas-phase absorption - 18 reactions is the [1,3]-dipolar cycloaddition of azomethine ylides, and the occurrence of C60 radical ions. Hamilton et al. which produces the so-called fulleropyrrolidines, in which the described the incorporation of C60 into channel-shape porous nitrogen and/or carbon atoms in the pyrrolidine ring can be sieves VPI-5 from benzene solutions. The composite showed 10 11 variously functionalized. However, except in few cases, even strong white light emission arising from the C60 molecules. 19 with very polar