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ChemComm
DOI: 10.1039/C3CC44418J
populated one to the aggregated species.14 Hence, there is a major
4
a) T. F. A. De Greef, M. M. J. Smulders, M. Wolffs, A. P. H. J.
Schenning, R. P. Sijbesma and E. W. Meijer, Chem. Rev. 2009, 109,
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15122.
contribution in emission from the monomeric state. To further
characterize the light emission of the supramolecular polymers
formed upon the selfꢀassembly of the NPDC 1, the commonly
used Commission International de l’ Eclairage (CIE) coordinates
were determined which are 0.26 and 0.40, resulting in a
chromaticity diagram that lays close to the white light region
centred at CIE coordinates of (0.33, 0.33) (Figure S5a).15
65
70
75
80
85
90
95
5
5
Finally, we measured the electrical conductivity (σ) of the gel
6
7
a) J. W. Steed, Chem. Commun. 2011, 47, 1379; b) A. Dawn, T.
Shiraki, S. Haraguchi, S.ꢀI. Tamaru and S. Shinkai, Chem. Asian J.
2010, 5, 266.
10 fibers formed by NPDC 1 in toluene by using FourꢀProbe
Conductivity (FPC) and conducting probe atomic force
microscopy (CꢀAFM).16 The undoped fibers formed by the selfꢀ
assembly of 1 show IꢀV response with calculated values of the
electric conductivity σ of 1.92 x 10ꢀ4 and 2.16 x 10ꢀ4 S/m for the
15 FPC and CꢀAFM techniques, respectively (Figure S5b,c). These
σ values are in the same range of those reported for organogels
prepared from wellꢀknown conductive materials like
tetrathiafulvalene or oligo(thiophenes).17
a) Y. Li, J. Gao, S. Di Motta, F. Negriand Z. Wang, J. Am. Chem.
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3686.
8
9
In summary, the luminescent and conducting properties of the
20 Nꢀannulated perylenedicarboxamide 1 that selfꢀassembles into 1D
supramolecular structures through Hꢀbonding interactions
between the amide functional groups and πꢀπ stacking of the
aromatic units are reported. The presence of the peripheral side
chains facilitates the bundling of the 1D supramolecular polymer
25 fibers to form an organogel. The cooperative supramolecular
polymerization of 1 in solution has been accurately analysed by
applying the recently described EQ model that allows to calculate
10 P. A. Korevaar, C. Schaefer, T. F. A. de Greef and E. W. Meijer, J.
Am. Chem. Soc. 2012, 134, 13482.
11 a) A. J. Markvoort, H. M. M. ten Eikelder, P. A. J. Hilbers, T. F. A.
de Greef and E. W. Meijer, Nat. Commun. 2011, 2, 509; b) H. M. M.
ten Eikelder, A. J. Markvoort, T. F. A. de Greef and P. A. J. Hilbers,
J. Phys. Chem. B 2012, 116, 5291.
12 Compound 1 is molecularly dissolved in 1 x 10ꢀ4 M solutions of
CHCl3 and toluene as demonstrate the same absorption pattern than
that observed in the corresponding UVꢀVis spectra at high
temperatures (see Figure S4).
0
the corresponding thermodynamic parameters (ꢀHelo = ꢀ62.78
0
kJmolꢀ1, ꢀS0 = ꢀ0.10 kJmolꢀ1, ꢀHnucl = ꢀ34.94 kJmolꢀ1, and a
30 cooperativity factor σ = 7.5 x 10ꢀ7). The aggregation state of
compound 1 strongly influences its optical properties resulting in
a broad band in the UVꢀVis spectrum. These changes also affect
the lightꢀemitting property and cover a broad range of the visible
spectral region in the aggregated state. The luminescent features
35 (with CIE coordinates of 0.26 and 0.40) together with the electric
conductivity (∼2 x 10ꢀ4 S/m) of the supramolecular polymers of 1
allow considering this simple compound as a soft material with
potential applicability in the research field of organic electronics
and photonics.
13 a) Ajayaghosh, A.; Vijayakumar, C.; Varghese, R.; George, S.,
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40
Financial support by the MINECO of Spain (CTQ2011ꢀ22581)
and UCM (UCMꢀSCHꢀPR34/07ꢀ15826) is acknowledged. F. G.
and J. B. are indebted to MEC and MINECO of Spain for a FPU
and FPI studentships, respectively. A.A. acknowledges the
Department of Atomic Energy, Government of India for an
110
2010, 132, 13206.
17 a) J. F. Hulvat, M. Sofos, K. Tajima and S. I. Stupp, J. Am. Chem.
Soc. 2005, 127, 366; b) T. L. Gall, C. Pearson, M. R. Bryce, M. C.
Petty, H. Dahlgaard and J. Becher, Eur. J. Org. Chem. 2003, 3562; c)
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Moriyama, K. Ito, and T. Kato, J. Am. Chem. Soc. 2005, 127, 14769;
d) J. PuigmartíꢀLuis, P. del Pino, E. Laukhin, J. Esquena, V. Laukhin,
C. Rovira, J. VidalꢀGancedo, A. G. Kanaras, R. J. Nichols, M. Brust
and D. B. Amabilino, Angew. Chem. Int. Ed. 2008, 47, 1861.
45 Outstanding Researcher Award and S. G is thankful to CSIR for a
research fellowship.
115
Notes and references
aDepartamento de Química Orgánica, Facultad de Ciencias Químicas,
Universidad Complutense de Madrid, 28040 Madrid (Spain).Fax: (+)
bPhotosciences and Photonics Group, Chemical Sciences and Technology
Division, CSIRꢁNational Institute for Interdisciplinary Science and
Technology (CSIRꢁNIIST), Trivandrumꢁ695019 (India). Eꢁmail:
55 † Electronic Supplementary Information (ESI) available: Figures S1ꢀS5
and experimental section. See DOI: 10.1039/b000000x/
1
2
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a) Especial issue on Organic Electronics, Adv Mater. 2013, 25, 1805;
b) M. O’Neill and S. M.; Kelly, Adv. Mater. 2011, 23, 566.
P. Samorí and F. Cacialli, Functional Supramolecular Architectures,
WileyꢀVCH, Weiheim, 2010.
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T. Aida, E. W. Meijer and S. I. Stupp, Science, 2012, 335, 813.
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