Journal of the American Chemical Society
ARTICLE
noncovalent character of weak triple H-bonding interactions
such as those established between complementary uracil and
2,6-di(acetylamino)pyridyl recognition moieties. In particular,
oligophenyleneethynylene molecular modules laterally equipped
with solubilizing aliphatic chains and peripherally bearing two
complementary hydrogen-bonding recognition units at their
extremities promote a self-assembly process generating supra-
molecular polymers that self-organize on the CNT surfaces in
nonpolar organic media and disassemble upon addition of polar
H-bond-breaking solvents (e.g., MeOH or DMSO). Unambig-
uous proofs of the formation of MWCNTs•[X•Y]n hybrids,
independent of their structure or geometry, have been provided
by several spectroscopic (absorption, emission, XPS), thermo-
gravimetric (TGA) and microscopic (TEM, AFM, STM) tech-
niques. Also, molecular modeling has been used to shed further
light on the self-organization process occurring between the
supramolecular polymers and the MWCNTs. In fact, if properly
functionalized, the supramolecular polymers introduced here can
be regarded as an alternative strategy to introduce desired
functionalities onto the CNT framework leaving unaltered its
structural, chemical, and physical properties. The methodology
presented in this manuscript is thus generic and can be extended
to other systems of interest opening up new avenues toward the
use of these carbon nanostructures in novel applications, such as
purification and separation of CNTs.
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’ ASSOCIATED CONTENT
S
Supporting Information. Detailed synthesis of molecular
b
modules and all experimental part. H and 13C NMR spectra.
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XPS and TGA analysis of hybrids. Photophysical investigations.
TEM and AFM of MWCNTs hybrids. This material is available
’ AUTHOR INFORMATION
Corresponding Author
Roberto.Lazzaroni@umons.ac.be; nicola.armaroli@isof.cnr.it;
’ ACKNOWLEDGMENT
This work was supported by the European Union through the
Marie Curie Initial Training Network “FINELUMEN” (grant
agreement PITNꢀGAꢀ2008ꢀ215399). D.B. and R.L. espe-
cially acknowledge the Belgian National Research Foundation
(FRSꢀFNRS, through the contracts no 2.4.625.08 F, F.4.505.10.
F, and 2.4.617.07.F), the “Loterie Nationale”, and the Rꢁegion
Wallonne through the “SOLWATT” program (contract no
850551). D.B. also thanks the “TINTIN” ARC project from
the Belgian French Community (contract no 09/14ꢀ023), the
University of Trieste, INSTM, and the University of Namur for
internal funding. N.A. thanks CNR (commessa PM.P04.010,
MACOL) and H.T. FRSꢀFNRS for his postdoctoral fellowship.
We are also grateful to Nanocyl for supplying the Nanocyl 7000
samples.
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