Liquid-Crystalline Fullerodendrimers which Display Columnar Phases Julie Lenoble, ² Natacha Maringa, ² Ste ´ phane Campidelli, ² Bertrand Donnio, ‡ Daniel Guillon,* ,‡ and Robert Deschenaux* ,² Institut de Chimie, UniVersite ´ de Neucha ˆ tel, AVenue de BelleVaux 51, Case Postale 158, 2009 Neucha ˆ tel, Switzerland, and Groupe des Mate ´ riaux Organiques, Institut de Physique et Chimie des Mate ´ riaux de Strasbourg, UMR 7504 (CNRS-ULP), 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France robert.deschenaux@unine.ch Received February 15, 2006 ABSTRACT The title compounds were synthesized by applying the 1,3-dipolar cycloaddition reaction of aldehyde-based poly(benzyl ether) dendrimers and sarcosine (N-methylglycine) to [60]fullerene (C 60 ). The dendritic building blocks used to functionalize C 60 displayed cubic and hexagonal columnar phases. The fullerene derivatives showed rectangular columnar phases of c2mm symmetry. The design of supramolecular [60]fullerene (C 60 ) assemblies, in which the [60]fullerene-containing molecular units are organized in a specific and controllable manner, is an elegant and appealing way to exploit the physical properties of C 60 in materials science (e.g., photoactive dyads and triads, 1 photovoltaic devices 2 ). Grafting dendrimers onto C 60 (ful- lerodendrimers) allowed this goal to be reached, as demon- strated by the formation of ordered and stable Langmuir and Langmuir-Blodgett films 3 and micelles. 4 Fullerene-contain- ing thermotropic liquid crystals 5-10 are promising chemical components for the development of nanotechnologies by the “bottom-up” approach (e.g., photoactive supramolecular switches 5c,h and supramolecular solar cell devices 5e ). Func- tionalization of C 60 with liquid-crystalline poly(arylester) dendrimers containing mesomorphic groups at the periphery by applying either the Bingel reaction 11 (from malonate ² Universite ´ de Neucha ˆtel. ‡ Institut de Physique et Chimie des Mate ´riaux de Strasbourg. (1) (a) Beckers, E. H. A.; van Hal, P. A.; Dhanabalan, A.; Meskers, S. C. J.; Knol, J.; Hummelen, J. C.; Janssen, R. A. J. J. Phys. Chem. A 2003, 107, 6218. (b) Atienza, C.; Insuasty, B.; Seoane, C.; Martı ´n, N.; Ramey, J.; Rahman, G. M. A.; Guldi, D. M. J. Mater. Chem. 2005, 15, 124. (c) Sa ´nchez, L.; Herranz, M. A Ä .; Martı ´n, N. J. Mater. Chem. 2005, 15, 1409. (d) de la Torre, G.; Giacalone, F.; Segura, J. L.; Martı ´n, N.; Guldi, D. M. Chem.sEur. J. 2005, 11, 1267. (2) (a) Eckert, J.-F.; Nicoud, J.-F.; Nierengarten, J.-F.; Liu, S.-G.; Echegoyen, L.; Barigelletti, F.; Armaroli, N.; Ouali, L.; Krasnikov, V.; Hadziioannou, G. J. Am. Chem. Soc. 2000, 122, 7467. (b) Imahori, H.; Fukuzumi, S. AdV. Funct. Mater. 2004, 14, 525. (c) van Duren, J. K. J.; Yang, X.; Loos, J.; Bulle-Lieuwma, C. W. T.; Sieval, A. B.; Hummelen, J. C.; Janssen, R. A. J. AdV. Funct. Mater. 2004, 14, 425. (d) Hoppe, H.; Egbe, D. A. M.; Mu ¨hlbacher, D.; Sariciftci, N. S. J. Mater. Chem. 2004, 14, 3462. (e) Winder, C.; Sariciftci, N. S. J. Mater. Chem. 2004, 14, 1077. (f) Hasobe, T.; Imahori, H.; Kamat, P. V.; Ahn, T. K.; Kim, S. K.; Kim, D.; Fujimoto, A.; Hirakawa, T.; Fukuzumi, S. J. Am. Chem. Soc. 2005, 127, 1216. ORGANIC LETTERS 2006 Vol. 8, No. 9 1851-1854 10.1021/ol0603920 CCC: $33.50 © 2006 American Chemical Society Published on Web 04/08/2006