Angewandte Chemie International Edition
10.1002/anie.202013474
RESEARCH ARTICLE
assembly (SASA
to the solvent and compared to the average in the fiber 1 (as
SASA (i)/<SASA >). Plotting these parameters we identify
defects in fiber 1, as those monomers which are more exposed to
the solvent and weaker incorporated in the assembly than the
average (Figure 4d, red dots). These defects are key for the
dynamics and monomer exchange in these fibers.32 Such defects
represent possible spots from which monomers 2 can enter fiber
1
(i)), which determines its degree of exposition
2020 research and innovation program (grant agreement n°.
818776 - DYNAPOL). L.D.C. thanks IUF and Axa for financial
support.The authors also acknowledge the computational
resources provided by the Swiss National Supercomputing
Center (CSCS) and by CINECA.
1
1
Keywords: Luminescence • Metal-metal interactions • Platinum
•
Self-assembly • Supramolecular chemistry
1
,
and thus pathways for 1-2 copolymerization and
3
5,36
interactions.
To explore the co-assembly of 2 onto a pre-formed fiber of 1
monomers, we then simulated a self-assembled fiber 1 immersed
in a solution (water:1,4-dioxane=60%:40%) containing dissolved
References
[
[
1]
2]
D. van der Zwaag, T. F. A. de Greef, E. W. Meijer, Angew. Chemie
Int. Ed. 2015, 54, 8334–8336.
2
monomers. We performed CG-MD simulations where fiber 1
(
composed of 400 assembled 1 monomers) is surrounded by a
X. Wang, G. Guerin, H. Wang, Y. Wang, I. Manners, M. A. Winnik,
Science 2007, 317, 644–647.
different number of 2 monomers (i.e., 50, 100 and 200). The
results of these simulations in Figure 4e demonstrate that the 2
monomers tend to form small aggregates, or stacks (in yellow),
which bind and nucleate onto the defects present on the surface
of fiber 1 (in red). The plot in Figure 4e shows that, in presence of
[3]
[4]
J. B. Gilroy, T. Gädt, G. R. Whittell, L. Chabanne, J. M. Mitchels, R.
M. Richardson, M. A. Winnik, I. Manners, Nat. Chem. 2010, 2, 566–
570.
2
monomers, the
1
monomers in the assembly reduce
M. E. Robinson, D. J. Lunn, A. Nazemi, G. R. Whittell, L. De Cola, I.
Manners, Chem. Commun. 2015, 51, 15921–15924.
Z. M. Hudson, D. J. Lunn, M. A. Winnik, I. Manners, Nat. Commun.
significantly their SASA and simultaneously increase their
interaction with the rest of the fiber 1. This is due to the binding of
[
[
5]
6]
2
with the most exposed monomers of fiber 1 (red monomers
2014, 5, 3372.
figure 4d), the effect becomes more and more relevant as the
number of 2 monomers in the system increased. This provides a
molecular-level picture in agreement with the coating
phenomenon detected by experiments. These results also
support the crucial role of structural defects in regulating the co-
Z. Yu, F. Tantakitti, T. Yu, L. C. Palmer, G. C. Schatz, S. I. Stupp,
Science 2016, 351, 497–502.
[
[
7]
8]
M. Wehner, F. Würthner, Nat. Rev. Chem. 2020, 4, 38–53.
S. Ogi, V. Stepanenko, K. Sugiyasu, M. Takeuchi, F. Würthner, J.
Am. Chem. Soc. 2015, 137, 3300–3307.
assembly, consistently with what recently evidenced in the study
of other supramolecular systems.32,37
[9]
J. Kang, D. Miyajima, T. Mori, Y. Inoue, Y. Itoh, T. Aida, Science
2015, 347, 646–651.
[
10]
S. Ogi, K. Sugiyasu, S. Manna, S. Samitsu, M. Takeuchi, Nat.
Chem. 2014, 6, 188–195.
Conclusion
[
[
[
11]
12]
13]
E. T. Powers, D. L. Powersy, Biophys. J. 2008, 94, 379–391.
A. Aliprandi, M. Mauro, L. De Cola, Nat. Chem. 2016, 8, 10–15.
S. Sinn, F. Biedermann, L. De Cola, Chem. - A Eur. J. 2017, 23,
Altogether, the X-ray determined structures have provided
insights into the self-assembly motifs of this kind of platinum
complexes revealing the structural factors driving the self-
recognition pathways revalorizing the important effects of the
modification of distant ancillary groups. In particular, we
presented, in real time, a supramolecular coating process of a
self-assembled structure by a different compound. Besides, our
experiments show how this process is reversible and that it
involves the direct interaction of the dissolved species with the
supramolecular self-assembled entities. All the self-assembly and
co-assembly processes are controlled by the composition of the
media and the latest occurs only in a very narrow range when the
water amount is between 50 and 65% revealing that the
environment in which the self-assembly takes place plays an even
more important role than the chemical design.
1965–1971.
[14]
M. Mauro, A. Aliprandi, C. Cebrián, D. Wang, C. Kübel, L. De Cola,
Chem. Commun. 2014, 50, 7269–7272.
[
[
15]
16]
V. W.-W. Yam, V. K.-M. Au, S. Y.-L. Leung, Chem. Rev. 2015, 115,
7589–7728.
M. H.-Y. Chan, M. Ng, S. Y.-L. Leung, W. H. Lam, V. W.-W. Yam, J.
Am. Chem. Soc. 2017, 139, 8639–8645.
[17]
M. Ward, Platin. Met. Rev. 2009, 53, 45–47.
[
[
[
[
18]
19]
20]
21]
Z. Chen, A. Lohr, C. R. Saha-Möller, F. Würthner, Chem. Soc. Rev.
2
009, 38, 564-584.
Y. Han, Z. Gao, C. Wang, R. Zhong, F. Wang, Coord. Chem. Rev.
020, 414, 213300.
2
K. Zhang, M. C.-L. Yeung, S. Y.-L. Leung, V. W.-W. Yam, Proc.
Natl. Acad. Sci. 2017, 114, 11844–11849.
Acknowledgements
K. Zhang, M. C. L. Yeung, S. Y. L. Leung, V. W. W. Yam, Chem
2
017, 2, 825–839.
G.M.-A. acknowledges the support of CONACYT-Mexico
Postdoctoral grant number 740732. P. Brüggeller thanks the
EFRE within the project SolarHydrogen for financial support. It is
funded by resources of the state of Tyrol together with the
European Union. G.M.P. acknowledges the funding received by
the Swiss National Science Foundation (SNSF grants
IZLIZ2_183336 and 200021_175735) and by the European
Research Council (ERC) under the European Union’s Horizon
[
[
22]
23]
Z. Li, Y. Han, F. Wang, Nat. Commun. 2019, 10, 3735.
V. C.-H. Wong, C. Po, S. Y.-L. Leung, A. K.-W. Chan, S. Yang, B.
Zhu, X. Cui, V. W.-W. Yam, J. Am. Chem. Soc. 2018, 140, 657–666.
J. P. Coelho, J. Matern, R. Q. Albuquerque, G. Fernández, Chem.
Eur. J. 2019, 25, 8960–8964.
[24]
[25]
[26]
Q. Wan, W.-P. To, X. Chang, C.-M. Che, Chem 2020, 6, 945–967.
G. Marinescu, S. Ferlay, N. Kyritsakas, M. Wais Hosseini, Chem.
6
This article is protected by copyright. All rights reserved.