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ChemComm
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COMMUNICATION
Journal Name
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Tobe and S. De Feyter, Angew. Chem. IDnOt.I:E1d0..,1203090/8D,04C7C,021982634F.
A. Ciesielski, P. J. Szabelski, W. Rżysko, A. Cadeddu, T. R. Cook,
P. J. Stang and P. Samorì, J. Am. Chem. Soc., 2013, 135, 6942.
Since the guest induced structural change was not observed
for a mixture of [12]DBA and [5]CMPA, the structural
recognition of [5]CMPA at the long side of [14]ISODBA (1.4 nm)
to [5]CMPA (1.0 nm) and adaptability of the alkoxy chains are
considered crucial elements, to maximize van der Waals
interactions between the host and guest molecules. Here we
briefly discuss the thermodynamic stability of the co-assembly
based on the comparison between Phase 1 and Co-crystal as
both appear in the same low-concentration range in TCB and
have the same unit cell area (16 nm2, Table S2, ESI).
Interaction energies of Phases 1-3 and Co-crystal are
analyzed by molecular mechanics (MM) simulations (see
ESI).36,37 As a result, Δh values that are enthalpy changes per
unit area upon formation of each phase become –23.5 and –
21.5 kcal·mol–1·nm–2 for Phase 1 and Co-crystal. This estimate
10 S.-B. Lei, K. Deng, Y.-L. Yang, Q.-D. Zeng, C. Wang and J.-Z.
Jiang, Nano Lett., 2008, 8, 1836.
11 J. Adisoejoso, K. Tahara, S. Okuhata, S. Lei, Y. Tobe and S. De
Feyter, Angew. Chem. Int. Ed., 2009, 48, 7353.
12 Y. Xue and M. B. Zimmt, J. Am. Chem. Soc., 2012, 134, 4513.
13 J. A. Theobald, N. S. Oxtoby, M. A. Phillips, N. R. Champness
and P. H. Beton, Nature, 2003, 424, 1029.
14 D. Bonifazi, S. Mohnani and A. Llanes-Pallas, Chem. Eur. J.,
2009, 15, 7004.
15 X. Zhang, Q. Zeng and C. Wang, Sci. China Chem., 2014, 57, 13.
16 K. Tahara, S. Lei, W.Mamdouh, Y. Yamaguchi, T. Ichikawa, H.
Uji-i, M. Sonoda, K. Hirose, F. C. De Schryver, S. De Feyter and
Y. Tobe, Y. J. Am. Chem. Soc., 2008, 130, 6666.
17 B. Schmaltz, A. Rouhanipour, H. J. Räder, W. Pisula and K.
Müllen, Angew. Chem. Int. Ed., 2009, 48, 720.
favoring Phase
1 does not support the experimental
18 M. Shen, Z. Luo, S. Zhang, S. Wang, L. Cao, Y. Geng, K. Deng,
D. Zhao, W. Duan and Q. Zeng, Nanoscale, 2016, 8, 11962.
19 K. Tahara, S. Furukawa, H. Uji-i, T. Uchino, T. Ichikawa, J.
Zhang, W. Mamdouh, M. Sonoda, F. C. De Schryver, S. De
Feyter and Y. Tobe, J. Am. Chem. Soc., 2006, 128, 16613.
20 Y. Tobe, K. Tahara and S. De Feyter, Bull. Chem. Soc. Jpn.,
2016, 89, 1277.
21 M. Lackinger and W. M. Heckl, Langmuir, 2009, 25, 11307.
22 S. Furukawa, K. Tahara, F. C. De Schryver, M. Van Der
Auweraer, Y. Tobe and S. De Feyter, Angew. Chem. Int. Ed.,
2007, 46, 2831.
observation where Co-crystal was formed preferably to Phase
1. Note that this enthalpy estimation does not include solvation
and also wetting energies, that would influence Co-crystal
formation.38,39 Another plausible factor is the difference in
entropy loss upon SAMNs formation. The numbers of the co-
adsorbed TCB and [5]CMPA molecules per the unit cells are
different between Phase 1 and Co-crystal (8 vs. 2).
In conclusion, we herein reported the formation and stable
co-assembly of pentagonal shaped molecule [5]CMPA and
isosceles triangle, alkoxy substituted [14]ISODBA at the
TCB/graphite interface. The structural recognition of [5]CMPA
at the long side of [14]ISODBA and the adaptability of alkyl
chain’s orientation due to de-symmetrized core of [14]ISODBA
are key elements for the formation of Co-crystal. Present study
provides useful information for structural control of self-
assembled systems formed by pentagonal molecules, which is
of importance in the field of 2D crystal engineering.
23 D. Bléger, D. Kreher, F. Mathevet, A.-J. Attias, G. Schull, A.
Huard, L. Douillard, C. Fiorini-Debuischert, F. Charra, Angew.
Chem. Int. Ed., 2007, 46, 7404.
24 M. Blunt, X. Lin, M. del C. Gimenez-Lopez, M. Schröder, N. R.
Champness and P. H. Beton, Chem. Commun., 2008, 2304.
25 J. Sun and S. Lei, J. Phys. Chem. C, 2018, 122, 12315.
26 M. Li, P. Xie, K. Deng, Y.-L. Yang, S.-B. Lei, Z.-Q. Wei, Q.-D. Zeng,
C. A. Wang, Phys. Chem. Chem. Phys., 2014, 16, 8778.
27 N. A. Wasio, R. C. Quardokus, R. P. Forrest, C. S. Lent, S. A.
Corcelli, J. A. Christie, K. W. Henderson and S. A. Kandel,
Nature, 2014, 507, 86.
28 T. Bauert, L. Merz, D. Bandera, M. Parschau, J. S. Siegel and K.-
H. Ernst, J. Am. Chem. Soc., 2009, 131, 3460.
29 B. E. Hirsch, S. Lee, B. Qiao, C.-H. Chen, K. P. McDonald, S. L.
Tait and A. H. Flood, Chem. Commun., 2014, 50, 9827.
30 K. Tahara, T. Balandina, S. Furukawa, S. De Feyter and Y. Tobe,
CrystEngComm, 2011, 13, 5551.
This work was supported by JSPS KAKENHI Grant Numbers
JP17H04794 and JP17K19130, the Fund of Scientific Research
Flanders (FWO), and KU Leuven - Internal Funds.
Conflicts of interest
31 B. Calmettes, S. Nagarajan, A. Gourdon, M. Abel, L. Porte and
R. Coratger, Angew. Chem. Int. Ed., 2008, 47, 6994.
32 J. Yamakawa, M. Ohkoshi, F. Takahashi, T. Nishiuchi, Y.
Kuwatani, T. Nishinaga, M. Yoshida and M. Iyoda, Chem. Lett.,
2008, 37, 784.
There are no conflicts to declare.
Notes and references
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37 K. Tahara, R. Nakayama, M. Maeda, S. De Feyter and Y. Tobe,
J. Phys. Chem. C, 2019, 123, 27020.
1
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M. O. Blunt, J. Adisoejoso, K. Tahara, K. Katayama, M. Van der
Auweraer, Y. Tobe and S. De Feyter, J. Am. Chem. Soc., 2013,
135, 12068.
A. Bellec, C. Arrigoni, G. Schull, L. Douillard, C. Fiorini-
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38 W. Song, N. Martsinovich, W. M. Heckl and M. Lackinger, J.
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39 R. A. Barnard and A. J. Matzger, Langmuir, 2014, 30, 7388.
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