ISMSC 2007 - Università degli Studi di Pavia

PSB 1
Rosette Nanotubes as Scaffolds for Stacked Multi-Porphyrin Assemblies
Darren A. Makeiff and Hicham Fenniri
Supramolecular Nanoscale Assembly Group, National Institute for Nanotechnology, University
of Alberta (Edmonton, Alberta, Canada)
E-mail: dmakeiff@ualberta.ca, hicham.fenniri@ualberta.ca
Hierarchical self-assembly is a highly attractive route to well-defined one-dimensional (1D)
chromophoric arrays, which may resemble natural antennae systems and display new and
interesting optical or electronic physical properties. 1 The G^C base is a DNA inspired
supramolecular synthon, which undergoes hierarchical self-assembly to form 1D nanostructures
called rosette nanotubes (RNTs). 2 Self-complementary hydrogen bonding arrays direct the
formation of hexamaric rosette supramacrocycles, 3 which can then form linear stacks up to a
millimeter long. 2 A simple strategy has been developed for functionalizing the surface of RNTs
through covalent modification of the G^C base backbone. Here we present the synthesis and
characterization of a porphyrin functionalized RNTs. RNTs are used as a rigid scaffold to
preorganize six peripheral porphyrin stacks to generate unique nanomaterials that are expected
to exhibit attractive photophysical and electronic properties for materials applications.
Porphyrin
G^C Base
Rosette Rosette Nanotubes
[1] Elemans, J. A. A. W.; Rowan, A. E.; Nolte, R. J. M. J. Mater. Chem. 2003, 13, 2661-2670.
[2] Fenniri, H.; Mathivanan, P.; Vidale, K. L.; Sherman, D. M.; Hallenga, K.; Wood, K. V.;
Stowell, J. G. J. Am. Chem. Soc. 2001, 123, 3854-3855.
[3] Marsh, A.; Silvestri, M.; Lehn, J. -M. Chem. Commun. 1996, 1527-1528.
PSB 2
Preparation and characterization of [60]fullerene fibrillar superstructures
and those polymerization by γ-ray irradiation
Sudip Malik, Norifumi Fujita, Seiji Shinkai
Department of Chemistry and Biochemistry, Graduale School of Engineering, Kyushu
University, 744 Moto-oka, Fukuoka, Japan
[60]Fullerenes are dissolved in solid and sublimable solvents such as naphthalene, ferrocene
and camphor, respectively. After removing these solvents by sublimation process the formation
of fibrillar superstructures of fullerene has been observed. The morphology of these
[60]fullerene superstructures has been investigated by scanning electron microscopy (SEM) as
shown in Figure 1. X-ray powder diffraction study and ATR/IR analysis show that [60]fullerene
superstructures preserve fcc lattice as like in pristine [60]fullerene. NMR together with elemental
analysis reveals the presence of significantly less amount of solvent in the superstructures. We
have attempted to polymerize these superstructures by γ-ray irradiation to achieve
poly[60]fullerene that is the material composed of only [60]fullerenes connected by covalent
bonds without any additional linkage.[1] We have characterized polymerized [60]fullerene by
TEM/HRTEM as well as spectroscopic analyses. This approach that provides not only an easy,
simple and efficient technique for the production of fibrous [60]fullerene or poly[60]fullerene but
also to control over the morphological aspects will be the promising pathways to prepare
fullerene-based material for the development of realistic applications.
(a) (b) (c)
1.67 µm 37.3 µm 1.67 µm
Figure 1: SEM images of [60]fullerene superstructure after sublimation of solid solvents :(a)
naphthalene, (b) ferrocene and (c) camphor, respectively.
Reference
[1] F. Giacalone and N. Martin, Chem. Rev., 2006, 106, 5136-5190.