Stepwise Adsorption of Alkoxy-Pyrene Derivatives onto a Lamellar, Non-Porous Naphthalenediimide-Template on HOPG

Article abstract of DOI:10.1002/chem.202004008

The development of new strategies for the preparation of multicomponent supramolecular assemblies is a major challenge on the road to complex functional molecular systems. Here we present the use of a non-porous self-assembled monolayer from uC₃₃-NDI-uC₃₃, a naphthalenediimide symmetrically functionalized with unsaturated 33 carbon-atom-chains, to prepare bicomponent supramolecular surface systems with a series of alkoxy-pyrene (PyrOR) derivatives at the liquid/HOPG interface. While previous attempts at directly depositing many of these PyrOR units at the liquid/HOPG interface failed, the multicomponent approach through the uC₃₃-NDI-uC₃₃ template enabled control over molecular interactions and facilitated adsorption. The PyrOR deposition restructured the initial uC₃₃-NDI-uC₃₃ monolayer, causing an expansion in two dimensions to accommodate the guests. As far as we know, this represents the first example of a non-porous or non-metal complex-bearing monolayer that allows the stepwise formation of multicomponent supramolecular architectures on surfaces.

Full text of DOI:10.1002/chem.202004008

Communication
doi.org/10.1002/chem.202004008
Chemistry—A European Journal
&
Supramolecular Chemistry
Stepwise Adsorption of Alkoxy-Pyrene Derivatives onto a
Lamellar, Non-Porous Naphthalenediimide-Template on HOPG
G. Henrieke Heideman+,[a] Josꢀ Augusto Berrocal+,[a, b] Meike Stçhr,[c] E. W. Meijer,*[b] and
Ben L. Feringa*[a]
at interfaces.[1–3] Besides novel assembly approaches and
Abstract: The development of new strategies for the
preparation of multicomponent supramolecular assem-
tuning of non-covalent interactions between distinct molecular
components, control over hierarchical organization along
blies is a major challenge on the road to complex func-
length scales is among the key topics. Both the design and
tional molecular systems. Here we present the use of a
characterization of multicomponent supramolecular systems
non-porous self-assembled monolayer from uC33-NDI-
uC33, a naphthalenediimide symmetrically functionalized
still present considerable challenges.[4,5] Organic–inorganic
hybrid systems like a self-healable supramolecular polymer,[6]
with unsaturated 33 carbon-atom-chains, to prepare bi-
nanoparticle assemblies,[7] or a dual-mode artificial muscle[8]
component supramolecular surface systems with a series
are illustrative examples for the non-covalent multicomponent
of alkoxy-pyrene (PyrOR) derivatives at the liquid/HOPG
synthesis approach.[9–13] Recent developments in supramolec-
interface. While previous attempts at directly depositing
ular block copolymers[14] have shown that combining (chiro)op-
many of these PyrOR units at the liquid/HOPG interface
failed, the multicomponent approach through the uC33-
NDI-uC33 template enabled control over molecular interac-
tions and facilitated adsorption. The PyrOR deposition re-
tical measurements, fluorescence imaging and computational
modeling can furnish insights into these complex multicompo-
nent systems.[15] However, such a deep level of understanding
and predictive value in complex systems design probably re-
structured the initial uC33-NDI-uC33 monolayer, causing an
mains confined to a few specific examples. Confined systems
expansion in two dimensions to accommodate the guests.
assembled at surfaces bring another level of complexity.[16–18]
As far as we know, this represents the first example of a
Surface-supported supramolecular assemblies at the liquid/
non-porous or non-metal complex-bearing monolayer
solid interface are typically studied by scanning tunneling mi-
that allows the stepwise formation of multicomponent
croscopy (STM), which allows to image (multicomponent) self-
assembled monolayers at quasi-molecular resolution.[1,19–25] Al-
supramolecular architectures on surfaces.
though the necessity to induce surface adhesion through
chemical design may limit the options to explore, surface-sup-
The creation of hierarchical materials and devices by bottom-
up molecular self-assembly requires the construction of multi-
component supramolecular systems and precise organization
ported multicomponent supramolecular systems were realized
resorting to a limited number of strategies. In particular,
porous self-assembled monolayers have received attention be-
cause of their preorganization.[26–39] One of the most attractive
features of this approach is its modularity, which allows control
over pore size and, hence, molecular dimensions of the
trapped guests.[39–45] Other reports have provided alternative
strategies based on host-guest interactions with metal com-
plexes.[46–48] Seeking for alternative strategies/molecular com-
ponents to allow the stepwise deposition of guest species is
key to further expand the fabrication of functional nanostruc-
tures and molecular defined surface systems.
[a] Dr. G. H. Heideman,+ Dr. J. A. Berrocal,+ Prof. B. L. Feringa
Stratingh Institute for Chemistry
University of Groningen
Nijenborgh 4, 9747 AG Groningen (The Netherlands)
E-mail: b.l.feringa@rug.nl
[b] Dr. J. A. Berrocal,+ Prof. E. W. Meijer
Institute for Complex Molecular Systems and
Laboratory of Macromolecular and Organic Chemistry
Eindhoven University of Technology
5600 MB Eindhoven (The Netherlands)
E-mail: e.w.meijer@tue.nl
Here we report on the templated deposition of pyrene de-
rivatives (PyrOR), PyrOMe, PyrSMe, PyrOEt, PyrOPr and
PyrOBu, on the non-porous self-assembled monolayer of the
[c] Prof. M. Stçhr
Zernike Institute for Advanced Materials
University of Groningen, 9747 AG Groningen, The Netherlands
[49]
long-carbon chain naphthalenediimide (NDI) uC33-NDI-uC33
[+] These authors contributed equally.
at the 1-phenyloctane/highly oriented pyrolytic graphite (1-
PO/HOPG) interface. The choice of the term “non-porous”
refers to the lack of preorganization of the initial uC33-NDI-
uC33 template. In other words, pristine uC33-NDI-uC33 monolay-
ers do not feature two-dimensional cavities—areas of uncov-
ered underlying HOPG substrate physically confined by uC33-
NDI-uC33—onto which the PyrOR guests can be physisorbed.
Supporting information and the ORCID identification number(s) for the au-
thor(s) of this article can be found under:
https://doi.org/10.1002/chem.202004008.
ꢀ 2020 The Authors. Published by Wiley-VCH GmbH. This is an open access
article under the terms of the Creative Commons Attribution License, which
permits use, distribution and reproduction in any medium, provided the
original work is properly cited.
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All the chemical structures investigated are shown in
Figure 1, whereas their syntheses and characterization are pre-
sented in the Supporting Information (Supporting Information,
pages S7–S14). Previous investigation highlighted the possibili-
ty to deposit pyrene moieties at the liquid/HOPG interface,
provided the simultaneous presence of other extended aro-
matic moieties in the chemical design.[35,50] Congruously, all our
attempts at the “untemplated” deposition of PyrOMe, PyrSMe,
PyrOEt and PyrOPr failed. The only exception was PyrOBu,
which forms self-assembled monolayers at the 1-PO/HOPG in-
terface (Supporting Information, Figure S4). Hence, we high-
light the use of our uC33-NDI-uC33 template as a tool to adsorb
and organize with nanometer precision alkoxy-pyrene deriva-
tives on HOPG.
Figure 2. STM image of uC33-NDI-uC33 at the 1-PO/HOPG interface, with a
schematic representation of the packing in which the orange rectangular
shapes represent the NDI core, the orange lines the carbon chains and the
orange dots the internal double bonds. The unit cell and the lattice parame-
ters[49] a, b and g are depicted in blue.
Figure 1. Chemical structures of PyrOMe, PyrSMe, PyrOEt, PyrOPr, PyrOBu,
and uC33-NDI-uC33
.
We recently showed that long carbon-chain NDIs (Cn-NDI-Cn)
featuring internal double bonds along the carbon-chain self-as-
semble at the 1-PO/HOPG interface into lamellar monolayers.
They comprise of alternating areas of NDI cores and carbon
tails, which appear as bright protrusions and darker regions, re-
spectively, in the STM images.[49] The internal double bonds
along the carbon chains could also be imaged in the darker
areas as additional bright protrusions symmetrically placed
with respect to the aromatic cores.[49] The simultaneous pres-
ence of EE-, EZ-and ZZ-configured isomers of uC33-NDI-uC33 did
not impede the formation of long-range ordered lamellar do-
mains, also due to the preferred physisorption for the less
abundant EE-configured molecules.[49] Preparation of uC33-NDI-
uC33 monolayers confirmed our previous results,[49] as shown
by the STM image and unit cell lattice parameters shown in
Figure 2. Right after having obtained the monolayer, we rinsed
the modified HOPG with n-octanoic acid (OA) to remove the
excess of uC33-NDI-uC33 that did not adhere to the substrate
and checked the preservation of the monolayer after the rins-
ing step by STM (Supporting Information, Figure S1).
Figure 3. STM images of uC33-NDI-uC33 monolayers after the deposition of:
a) PyrOMe (OA/HOPG interface; 25 nmꢂ25 nm, Vtip =1 V, Iset =50 pA);
b) PyrSMe (OA/HOPG interface; 35 nmꢂ35 nm, Vtip =1 V, Iset =100 pA);
c) PyrOMe (1-PO/HOPG interface; 35 nmꢂ35 nm, Vtip =1 V, Iset=60 pA);
d) PyrSMe (TD/HOPG interface; 35 nmꢂ35 nm, Vtip =1 V, Iset =100 pA). The
schematic unit cell of the PyrOMe/uC33-NDI-uC33 bicomponent system is
displayed as a blue rectangle in Figure 3a as a guide to the eye.
contrast deriving from the substitution of the heteroatom in
the (thio)ether linkage. Similar STM images were recorded,
with the new bright dots ascribed to PyrSMe staying next to
the NDI cores in a zipper-like fashion (Figure 3b). Replacing OA
with 1-PO or n-tetradecane (TD) consistently afforded the
same results with both PyrOMe (Figure 3c) and PyrSMe (Fig-
ure 3d), suggesting no influence of the solvent(s) chosen to
form the bicomponent system and the robustness of the mul-
ticomponent co-assembly. Time monitoring of the sequential
adsorption of PyrOMe/PyrSMe onto the uC33-NDI-uC33 tem-
plate suggested the occurrence of nucleation processes: low
Next, the rinsed uC33-NDI-uC33 monolayer was treated with
a PyrOMe solution in OA. STM imaging of the newly treated
surface revealed the presence of new protrusions placed in a
zipper-like fashion alongside the NDI cores of the original la-
mellar morphology (Figure 3a). These new protrusions were
more extended and brighter than the internal double bonds of
uC33-NDI-uC33 of Figure 2.
Intrigued by this preliminary result, we repeated the experi-
ment with PyrSMe, the sulfur analogue of PyrOMe, to examine
the possible consequences on both adsorption and imaging
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coverages by PyrOMe/PyrSMe were imaged at the initial
stages of the process (5 min), with clear surface regions show-
ing only the initial uC33-NDI-uC33 monolayer (Supporting Infor-
mation, Figure S2). Prolonged exposure (3–4 hours) of the
uC33-NDI-uC33 template to the PyrOMe/PyrSMe solutions re-
sulted in quantitative coverage (Figure 3).
the high selectivity of the uC33-NDI-uC33 monolayer is not un-
derstood, but it certainly highlights a “unique” character for
this particular template. Importantly, all the experimental re-
sults on co-assembly obtained with the uC33-NDI-uC33 mono-
layer were highly consistent and reproducible.
Further insights into the system were obtained by analyzing
the profile plots of the STM images obtained during the early
stages (5 min) of the PyrSMe adsorption (Figure 5). The cover-
age of the uC33-NDI-uC33 adlayer by PyrSMe was not quantita-
tive during the initial stages of the process. Thus, the STM
images displayed the simultaneous presence of the uC33-NDI-
uC33 lamellae similar to Figure 2, and additional protrusions
positioned in a zipper-like fashion with respect to the NDI
cores as in Figures 3 and 4 (STM image of Figure 5). Profile
plots measured over lengths of approximately 42 nm in both
surface areas, that is, with and without adsorbed PyrSMe,
highlighted remarkable differences in the periodical organiza-
tions. The underlying uC33-NDI-uC33 template was highly regu-
lar and consistent with an about 5 nm periodical lamellar mor-
phology in accordance with our previous report[49] (orange
trace in Figure 5, bottom). The profile plot of the surface area
featuring the adsorbed PyrSMe showed less regularity, al-
though a clear increase in the distance between the maxima
was noticeable (cyan trace in Figure 5, top). The presence of 7
maxima in 42 nm resulted in a 6 nm average distance between
parallel arrays in the surface areas with PyrSMe. This suggest-
ed that the parallel NDI cores increased their distance by ap-
Having demonstrated the consistency of our systems over a
broad scope of solvents (OA, 1-PO and TD), we introduced
subtle structural modifications in the PyrOR molecular design.
Extending the length of the alkyl chain by one (PyrOEt) or two
(PyrOPr) carbon atoms resulted in the same outcome ob-
served with PyrOMe and PyrSMe, namely the zipper-like depo-
sition of the pyrene derivatives alongside the NDI cores of
uC33-NDI-uC33 (Figure 4a for PyrOEt, Figure 4b for PyrOPr). In
stark contrast, PyrOBu offered only modest signs of adsorption
onto the uC33-NDI-uC33 template at ca. 10À2 m concentrations
(Supporting Information, Figure S4). A ten-fold increase in con-
centration resulted in the displacement of uC33-NDI-uC33 and
subsequent formation of a new monolayer uniquely formed by
PyrOBu, instead (Supporting Information, Figure S4). Such ob-
servation suggested that the competition between stepwise
adsorption onto the uC33-NDI-uC33 template and alkoxy-
pyrene monolayer formation is controlled by the subtle inter-
play of different parameters, which certainly include concentra-
tion and adsorption energy of the alkoxy-pyrenes on HOPG.
This balance becomes particularly evident in the case of
PyrOBu, which features a longer alkyl chain and likely en-
hanced van der Waals interactions, since the other PyrOR in-
vestigated do not form monolayers at the liquid/HOPG inter-
face. Indeed, the use of more concentrated (saturated) solu-
tions of PyrOMe, PyrSMe, PyrOEt and PyrOPr did not affect
their adsorption onto the uC33-NDI-uC33 template.
In addition, we tested other potential templates from the
[49,51]
unsaturated and saturated Cn-NDI-Cn
family to elucidate
essential structural parameters (the complete list of Cn-NDI-Cn
tested is reported in Figure S5). Surprisingly enough, although
these compounds are structurally very similar to uC33-NDI-
uC33, their assistance towards subsequent adsorption of the
PyrOR compounds was extremely modest. The case of C33-
[49]
NDI-C33 (Figure S5), which only differs from uC33-NDI-uC33 by
the absence of the internal double bonds in the chemical
structure, is particularly remarkable. Currently, the reason for
Figure 5. Profile plots measured over approximately 42 nm of the STM
image (middle) of PyrSMe adsorption within the uC33-NDI-uC33 template in
OA (Vtip =1 V, Iset =50 pA), showing seven maxima (6 nm periodicity) after
adsorption of PyrSMe (top, cyan) and eight maxima (5 nm periodicity) in the
original uC33-NDI-uC33 monolayer (bottom, orange).
Figure 4. STM images after the sequential deposition onto the uC33-NDI-
uC33 template in OA of: a) PyrOEt (25 nm ꢂ 25 nm, Vtip =1 V, Iset =10 pA),
and b) PyrOPr (25 nmꢂ25 nm, Vtip =1.4 V, Iset =15 pA).
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proximately 1 nm to host PyrSMe and form the bicomponent
system.
enes and NDI cores cannot be excluded within the bicompo-
nent system. However, a hypothesis on the exact geometry
would be speculative due to the unknown orientation of the
pyrene derivatives and awaits in depth computational studies.
Nevertheless, it should be emphasized that the positioning of
alkoxy-pyrenes alongside the NDI cores, and not in the typical
stacked donor-acceptor configuration occurring in charge-
transfer solution-phase supramolecular systems,[53] is a unique
aspect of our system.
Combining all the information obtained, we formulate a
schematic pictorial representation for the PyrOMe/uC33-NDI-
uC33 bicomponent system (Figure 6). Although the clear-cut
image in Figure 5 features PyrSMe, the qualitative model was
built for PyrOMe due to the larger statistics available for such
PyrOR. While the cartoon depicts a regular system, we would
like to stress that analysis of the STM images revealed fluctua-
tions in the molecular arrangement. Hence, the illustration in
Figure 6 should be taken as a qualitative description rather
than an unambiguous unit cell of the PyrOMe/uC33-NDI-uC33
monolayer. Moreover, the orientation of the alkoxy-pyrene
moieties was arbitrarily chosen in our qualitative model due to
the lack of precise information obtained from the STM images.
A previous model to explain the deposition of pyrenes in
porous templates followed the same approach.[52] Statistical
analysis on a number of STM images of the PyrOMe/uC33-NDI-
uC33 system allowed to estimate an aPyrOMe value as high as
6.05Æ0.15 nm (averaged value for the assemblies in 1-PO and
OA), whereas the a unit cell parameter for the original uC33-
NDI-uC33 monolayer is 5.27Æ0.08 nm (a is shown in
Figure 2).[49] The enhancement of the lateral distance between
two rows of NDIs in the bicomponent system (aPyrOMe) pointed
to a lateral expansion of the initial uC33-NDI-uC33 monolayer to
accommodate PyrOMe. Since the unsaturated carbon chains
of uC33-NDI-uC33 have a strong preference for interdigita-
tion,[49] we hypothesize that such lateral expansion necessarily
pulls the carbon chains apart and creates exposed pockets at
well-defined distances on the underlying HOPG substrate,
while partially retaining the interdigitation of the template
molecules. The lattice expansion along the a vector appears to
reach a maximum limit, which explains the decreased adsorp-
tion of PyrOR upon chain extension. A further expansion along
the b direction is also necessary to favor the adsorption of
PyrOMe, modifying the b unit cell parameter from 0.94Æ
0.06 nm to an average value 1.84Æ0.22 for bPyrOMe (obtained
from the statistical analysis of a number of STM images 1-PO
and OA). The two-dimensional expansion of the uC33-NDI-uC33
template is in line with the lack of preorganization of the initial
monolayer. Indeed, the latter must adapt to the presence of
the PyrOR species and create the pockets for their adsorption.
Additional stabilizing intermolecular interactions between pyr-
In conclusion, we presented the stepwise adsorption of
alkoxy-pyrene derivatives PyrOMe, PyrSMe, PyrOEt, PyrOPr
and PyrOBu onto a lamellar, non-porous uC33-NDI-uC33 tem-
plate on HOPG. The deposition of these alkoxy-pyrenes brings
to the formation of a bicomponent system that appears dra-
matically different from the initial monolayer upon STM imag-
ing. New bright protuberances (the alkoxy-pyrenes) are
imaged in a zipper-like fashion alongside the NDI cores. More-
over, the formation of a bicomponent system significantly
alters the organization of the initial uC33-NDI-uC33 template,
causing an expansion in both directions of the original unit
cell directions to accommodate the guest in the template. To
the best of our knowledge, the uC33-NDI-uC33 template is the
first self-assembled monolayer that allows for the stepwise
construction of on-surface multicomponent supramolecular ar-
chitectures without resorting to the preorganization of porous
architectures or host-guest interactions with metal-complexes.
This offers a unique approach to establish future directions of
supramolecular surface chemistry through stepwise multicom-
ponent assembly. Current efforts of our joined research pro-
gram focus on the use of the uC33-NDI-uC33 template as a mo-
lecular track for the controlled unidirectional translation of
light-driven molecular motors on surfaces.
Acknowledgements
This work was supported financially by the European Research
Council (ERC, advanced grant no. 694345 to B.L.F.), and the
Ministry of Education, Culture and Science (Gravitation Pro-
gram no. 024.001.035 to E.W.M. and B.L.F.). Bas F. M. de Waal
(TU Eindhoven) is acknowledged for providing the starting
amine for the synthesis of uC33-NDI-uC33.
Conflict of interest
The authors declare no conflict of interest.
Keywords: adsorption · internal double bonds · long chain-
naphthalenediimides
·
multicomponent
self-assembled
monolayers · non-porous templates
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Manuscript received: September 2, 2020
Accepted manuscript online: September 7, 2020
Version of record online: && &&, 0000
Chem. Eur. J. 2020, 26, 1 – 6
www.chemeurj.org
5
ꢁ 2020 The Authors. Published by Wiley-VCH GmbH
&
&
These are not the final page numbers! ÞÞ

Communication
doi.org/10.1002/chem.202004008
Chemistry—A European Journal
COMMUNICATION
Supramolecular surface systems: A
non-porous monolayer of a long-carbon
chain naphthalenediimide serves as
template for the stepwise adsorption of
a series of alkoxy-pyrene derivatives at
the liquid/HOPG interface. Depositing
the guests onto the template causes a
severe reorganization of the initial mon-
olayer, as visualized by scanning tunnel-
ing microscopy.
&
Supramolecular Chemistry
G. H. Heideman, J. A. Berrocal, M. Stçhr,
E. W. Meijer,* B. L. Feringa*
&& – &&
Stepwise Adsorption of Alkoxy-Pyrene
Derivatives onto a Lamellar, Non-
Porous Naphthalenediimide-Template
on HOPG
&
&
Chem. Eur. J. 2020, 26, 1 – 6
www.chemeurj.org
6
ꢁ 2020 The Authors. Published by Wiley-VCH GmbH
ÝÝ These are not the final page numbers!