Supramolecular Electropolymerization

Article abstract of DOI:10.1002/anie.201809756

Gaining control over supramolecular polymerization mechanisms is of high fundamental interest to understand self-assembly and self-organization processes at the nanoscale. It is also expected to significantly impact the design and improve the efficiency of advanced materials and devices. Up to now, supramolecular polymerization has been shown to take place from unimers in solution, mainly by variations of temperature or of concentration. Reported here is that supramolecular nucleation-growth of triarylamine monomers can be triggered by electrochemistry in various solvents. The involved mechanism offers new opportunities to precisely address in space and time the nucleation of supramolecular polymers at an electrode. To illustrate the potential of this methodology, supramolecular nanowires are grown an oriented over several tens of micrometers between different types of commercially available electrodes submitted to a single DC electric field, reaching a precision unprecedented in the literature.

Full text of DOI:10.1002/anie.201809756

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Accepted Article
Title: Supramolecular Electropolymerization
Authors: Thomas K Ellis, Mélodie Galerne, Joseph J. Armao IV, Artem
Osypenko, David Martel, Mounir Maaloum, Gad Fuks, Emilie
Moulin, Odile Gavat, and Nicolas Giuseppone
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201809756
Angew. Chem. 10.1002/ange.201809756
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http://dx.doi.org/10.1002/ange.201809756

10.1002/anie.201809756
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Supramolecular Electropolymerization
Thomas K. Ellis,§ Melodie Galerne,§ Joseph J. Armao IV, Artem Osypenko, David Martel, Mounir
Maaloum, Gad Fuks, Emilie Moulin, Odile Gavat, and Nicolas Giuseppone*
Abstract: Gaining control over supramolecular polymerization
mechanisms is of high fundamental interest to understand self-
assembly and self-organization processes at nanoscale. It is also
expected to significantly impact the design and improve the efficiency
of advanced materials and devices. Up to now, supramolecular
polymerization has been shown to take place from unimers in solution,
mainly by variations of temperature or of concentration. Here we show
that supramolecular nucleation-growth of triarylamine monomers can
be triggered by electrochemistry in various solvents. The involved
mechanism offers new opportunities to precisely address in space
and time the nucleation of supramolecular polymers at an electrode.
To illustrate the potential of this methodology, we grow and orient
supramolecular nanowires over several tens of micrometers in
between different types of commercially available electrodes
proved to involve a nucleation/growth process composed of four
elementary steps: (i) photoexcitation of a catalytic amount of
triarylamines and subsequent oxidation to their radical cations,
with concomitant reduction of the chlorinated solvent producing
chloride counterions; (ii) formation of
a
nucleus of
triarylammonium radicals in a double columnar arrangement
involving hydrogen bonds; (iii) stacking of neutral triarylamines
onto the nucleus and subsequent growth of the primary fibril;
(iv) lateral secondary aggregations of fibrils by van der Waals
forces to reach larger bundles of fibers.
Based on this mechanism, we envisioned to suppress the light-
irradiation step and to replace it by a direct electrochemical
oxidation (Figure 1a). We first checked the possibility to oxidize 1
using light irradiation in the presence of a high concentration of
commonly used electrolytes ([1] = 1 mM; [electrolyte] = 100 mM
in 1,1,2,2-tetrachloroethane (TCE)). By probing the system with
UV-Vis-NIR spectroscopy, we confirmed the effective photo-
induced oxidation in the presence of tetrabutylammonium
perchlorate (TBAClO4), hexafluorophosphate (TBAPF6), or
chloride (TBACl) (section S5.1, Figure S5). Indeed, as already
described extensively,[8,11] one of the typical signatures
submitted to
a single DC electric field, reaching a precision
unprecedented in the literature.
Because supramolecular bonds are labile in essence,
supramolecular polymers are highly dynamic chemical objects.[1,2]
The kinetics of formation and dissociation of such polymers can
be partially controlled by intensive parameters (e.g. temperature,
concentration, mechanical stress) or by modifying in situ their
supramolecular recognition units.[3] This toolbox is of particular
interest for the design of responsive materials.[4,5] However, one
drawback of such an intrinsic dynamics is that gaining control over
their polydispersity index is particularly difficult. To improve that
aspect, recent seminal works have been developed to access
living supramolecular polymerization processes.[6,7] Another very
challenging aspect of supramolecular polymerization concerns its
precise control in space (i.e. with a spatial resolution approaching
the size of the polymer itself). In this direction, the possibility to
precisely address the nucleation and growth of supramolecular
polymers by electrochemistry attracted our attention.
+
associated to radical cation 1• , and further to the self-assembly
process, is the appearance of a stable absorption band around
750 nm (Figure 1b, dashed line). We then performed cyclic
voltammetry (CV) at a scan rate of 100 mV∙s-1 for TAA 1 in TCE
and in the presence of TBAPF6 (Figure 1c), showing a first
oxidation associated with radical cation 1•+ (E1/2 = -71 mV), and a
second oxidation leading to the corresponding dication 12+ (E1/2
=
704 mV).[13] Spectroelectrochemistry was also performed on this
solution, showing the expected UV-Vis spectrum of 1•+ as it
passes over the first oxidation potential (Figure 1d). The resulting
spectrum perfectly matches with the one observed upon photo-
irradiation (Figure 1b, plain line). We further tested whether the
wires can self-assemble electrochemically from 1 and 1•+ in the
presence of the electrolyte and in the dark. For that, we probed
by 1H NMR spectroscopy the behavior of a solution of 1 in
deuterated chloroform (5 mM) and in the presence of TBAPF6
(100 mM), while holding a potential of 0.2 V vs Fc/Fc+ (Ferrocene
/ Ferrocenium reference redox couple) for 30 min. This time
period of electro-oxidation involves the production of
approximately 1% of 1•+ in the solution as determined by
The rational design of the present study rests on the
supramolecular polymerization of triarylamine molecules (TAA)
substituted with (an) amide function(s), such as molecule 1 in
Figure 1.[8–10] We have previously shown that, in chlorinated
solvents, light-triggered oxidation of TAA to the corresponding
+
radical cation (TAA• ) can promote supramolecular polymerization.
The associated mechanism was thoroughly investigated by a
number of experimental and theoretical means,[11,12] and it was
1
coulometry (section S5.2. Figure S7). H NMR spectrum shows
that, after this electrochemical treatment at constant
concentration and temperature, the aromatic proton resonance
signals of the triarylamine fully disappear. A similar behavior was
observed when electro-oxidation of 1 was performed in the
absence of electrolyte with a high potential of 25 V held for 30 min
[a]
Dr. Thomas K. Ellis, Melodie Galerne, Dr. Joseph J. Armao IV, Dr.
Artem Osypenko, Dr. David Martel, Prof. Dr. Mounir Maaloum, Dr.
Gad Fuks, Dr. Emilie Moulin, Odile Gavat, and Prof. Dr. Nicolas
Giuseppone*
in TCE-d (Figure S8a). The disappearance of the NMR signals
2
SAMS research group – University of Strasbourg – Institut Charles
Sadron, CNRS – 23 rue du Loess, BP 84047, 67034 Strasbourg
Cedex 2, France
E-mail: giuseppone@unistra.fr
Website: http://sams.ics-cnrs.unistra.fr/
after the oxidation of a small percentage of the triarylamine
molecules is a typical signature of a nucleation step involving
radical cations and followed by the formation of large and rigid
anisotropic stacks involving all the remaining neutral TAAs as
elucidated in our previous works.[8,11]
§
These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of
the document.
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Drop cast samples from this solution were also imaged by both
TEM and AFM, confirming the formation of bundled
supramolecular triarylamine nanowires (Figure 1e and S8b). By
the following study), and that it forms a thermo-responsive fibrillar
organogel upon subsequent cooling (with an onset gelation
concentration of 2.5 mg/mL at T ≈ 10 ˚C) (Figure 2a). A peculiar
property of this thermal transition is its large hysteresis showing a
good stability of the gel when heating up to T ≈ 30 °C (Figure S13).
By making use of this hysteresis, we found that at 20°C the
supramolecular fibers formation can be triggered by electro-
activation from solution. Indeed, by introducing a 5 mg/mL
solution of 1 between 5 μm path sealed ITO plates (which avoids
evaporation), and after application of a DC field of 1 x 107 V∙m-1,
we observed the formation of a dense array of fibers by polarized
optical microscopy (POM) (Figure 2b). We subsequently
questioned whether fibers formation within the electrical field
requires an electrical contact at the electrode to start nucleation.
A blocked ITO layer device coated with a photoresist did not show
fibers formation, except at the edges that contain flaws in the
photoresist (Figure S2c). The necessity of the electrical contact
for complete wire formation indicates that, even without
electrolyte, the immediate contact with the electrode in such high
field is able to create an oxidized seeding surface from which
neutral TAA can grow. In addition, the continuous growth of
individual fibers from the electrode edges across the solution is
also highlighting that the fibers formation is clearly not triggered
by a sol-gel transition (Figure 2c, and section S10).
analogy with our previous investigations involving
a
photogenerated radical cation[11] and accordingly to a series of
control experiments (see sections S6-S8 in the supporting
information), we can conclude that the electrochemically triggered
self-assembly mechanism involves the following sequence
(Figure 1f): (i) diffusion of neutral molecule 1 into the double layer,
(ii) oxidation of the neutral species at the electrode surface
producing 1•+, (iii) migration of the radical cation into the diffusion
layer, (iv) nucleation of the radical species, and (v) growth of the
supramolecular fibers by addition of neutral monomers onto the
nuclei.
We then turned our investigations towards gold interdigitated
electrodes (IDEs) of lateral geometry, separated by parallel gaps
of 10 m, and in the presence of a DC electric field. The
substrates were analyzed by POM, SEM, and AFM, all showing
the homogeneous alignment of mono-disperse fibers filling all
gaps with an orientation parallel to the applied electric field (Figure
2d-f). Using this set-up configuration, we first determined
unambiguously that the fibers formation is the result of an electro-
oxidation and does not come from thermal or concentration
effects. Indeed, a first control experiment without an electric field
revealed only the presence of amorphous and unlocalized
material (Figure S14). Thus, in the time span needed for the
solvent to evaporate, the nucleation-growth process does not take
place, which also excludes the involvement of dielectrophoretic
alignment processes. In a second control experiment, a solution
that had been previously allowed to form a gel at low temperature
was partly re-solubilized with a gentle heating at 30 °C. At this
temperature, although being macroscopically in the sol state,
fibers seeds remain in suspension. However, after drop-casting
on the IDEs in absence of an electric field and evaporation of the
solvent, only a disordered network of fibers was observed (Figure
S15a). In addition, application of an electric field of 1.25 x 107 V∙m-
1 for duration of 5 minutes after deposition and concentration to
the gel state by solvent evaporation, did not show any further
alignment (Figure S15b). This last observation indicates that the
reorientation of the fibers after entanglement in a low mobility
medium is not possible.
Figure 1. (a) Electro- or photo-triggered oxidation of TAA 1 in its radical cation
1•+; (b) Normalized absorption spectra of electro- and photo-oxidized solutions
of 1 at a concentration of 1 mM in TCE and in the presence of 0.1 M TBAPF6;
(c) CV data of compound 1 at a concentration of 1 mM in TCE with 100 mM
TBAPF6 and at a scan rate of 0.1 V∙s-1; (d) Spectroelectrochemical behavior of
1 for different potential scans over the first oxidation wave in the range -0.15 to
0.15 V vs Fc/Fc+ in TCE with 100 mM TBAPF6; (e) (i) TEM and (ii) AFM height
images of the supramolecular fibers formed from 1 by an electrochemically
triggered process; (f) Simplified electrochemical mechanism of the (nucleation /
growth) supramolecular polymerization process activated by electro-oxidation.
Knowing the possibility to electrochemically trigger the
nucleation/growth of supramolecular triarylamines in solution, we
then investigated the possibility to directly interconnect
commercially available microelectrodes in the presence of a sole
Direct Current (DC) electric field, without electrolyte. However,
when using chloroform or 1,1,2,2-tetrachloroethane to dissolve
TAA molecules, we were unable to grow nanowires at low
voltages (probably because of the difficulty to form 1•+ in the
absence of electrolyte), neither to align them at higher voltages
due to short-circuits (probably because of the red-ox activity of the
chlorinated solvent itself). Interestingly, we found that TAA 1 can
dissolve at elevated temperatures in alkanes (such as heptane in
Overall, these series of experiments in vertical sealed ITO cells
and horizontal gold IDEs configurations reveal that (i) the
successful polymerization procedure involves electro-oxidation of
TAA 1 at the electrode surface as the sole cause for localized
nucleation of fibers, and that (ii) the good alignment of these fibers
requires their oriented supramolecular growth in the electric field
before the formation of a kinetically trapped disordered entangled
network.
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Figure 2. (a) TEM image of the fibrillar organogel of TAA 1 in heptane; (b) Cross-polarized optical microscopy image of supramolecular polymers formed between
ITO plates: a 5 mg/mL solution was let to cool down to room temperature before deposition into the ITO cell with a path of 5 μm, and the solution was subsequently
subjected to a DC electric field to trigger the supramolecular polymerization; (c) Cross-polarized optical microscopy image of a cell reproducing the protocol described
in (b), but using blocked ITO electrodes, avoiding the electrochemically triggered formation of the supramolecular polymers, except at the edge of the ITO domain;
(d-f) POM (d), SEM (e) and AFM (f) images of IDEs after drop-casting a 5 mg/mL solution of 1 and under application of an electric field of 1.25 x 107 V∙m-1; (g)
Topological representation of the AFM image shown in (f); (h) 3D schematic depiction of the supramolecular electropolymerization process occurring between IDEs
and following the electric field lines as observed in (g) (the green and red ovals represent 1 and 1•+, respectively).
Our description of the self-organization process in the DC field is
reinforced by the observation that the nucleation starts always
from the anode (+ electrode) with the fibers growing towards the
cathode (‒ electrode), as clearly shown by SEM and AFM on
Figures 3a and 3c. Nucleation/growth at anode was in addition
visualized by a real time movie in the interdigitated configuration
(Supplementary Movie 1, and section S11.5). Another striking
feature of this process is illustrated by the precise topology of the
bridging fibers observed by AFM (Figure 2g) and showing that the
supramolecular polymers are strictly following the curvature of the
electric field during their growth (Figure 2h).
We then studied the effects of field strength and concentration on
fibers polymerization and alignment. We determined that the
minimum field strength required for the polymerization is Ef ≈ 1 ×
106 V∙m-1. However, with such a field, the fibers are still highly
disordered (Figure S17a,b). Alignment started to occur at 5 × 106
V∙m-1 and was found to be optimal at 1.25 × 107 V∙m-1 (Figure
S17c,d). For the optimal voltage, we determined that a minimal 2
mg/mL concentration of TAA leads to isolated fibers spanning the
entire gap (Figure S16). A higher concentration of 5 mg/mL
resulted systematically in fully filled electrode gaps with dense
bundles of fibers, with some isolated fibers passing through the
cathode (Figure 2e). We quantified the degree of alignment by
calculating the order parameter S (0 ≤ S ≤ 1) as a function of the
electric field value (Figure 3b, and section S12). At a voltage of
1.25 × 107 V∙m-1, we found average order parameters of
0.94±0.08 for single fibers spanning the entire gap (2 mg/mL)
(Figure 3d) and of 0.87±0.09 for single fibers spanning the
negative electrodes (5 mg/mL) (Figure S23). This means that high
TAA concentration increases the number of fibers spanning the
gaps without modifying the very high quality of the alignment. In
addition, by applying an electric field to a device with a more
complex geometry, that is using circular concentric interdigitated
electrodes, we unambiguously proved that the wires precisely
follow in any point the field’s lines (Figures S18 a-c).
As a last implementation, using microarray electrodes, we were
able to grow single supramolecular wires between two pores of
less than 5 m in diameter and over a distance of 50 m in length
(Figure 3d). The POM image confirms the nucleation from the
anode and the fiber growth towards the cathode only when the
pores align in the DC field direction. To the best of our knowledge,
such a precise bridging configuration is unprecedented in the
literature, either by using top-down techniques such as zone-
casting[14] or by orienting organogelators[15] and liquid crystal
polymers[16–19] in an AC field.
In addition, our previous method consisting in the photo-triggered
supramolecular polymerization of triarylamine between
nanoelectrodes[20] is not adapted to the various configurations of
the present study. First, photo-oxidation appeared experimentally
limited to path lengths below 100 nm, a distance almost three
orders of magnitude smaller compared to the present devices. We
postulate that this limitation partly comes from the necessary use
of chlorinated solvents to trigger TAA oxidation with light. Indeed,
the large electric field necessary to align the wires on long
distances would be shielded by the high amount of photo-
generated triarylamonium radical cations and their respective
chloride counter ions. If this effect can indeed be overcome by
using nanoelectrodes in which the Debye length is larger than the
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electrode gap, it precludes using photo-oxidation for higher path
lengths (section S13). In addition, in our previous approach,[20]
fibers were grown everywhere in solution, necessitating the
removing of unattached fibers all over the device. Here, making
placement and orientation of supramolecular polymers in
between electrodes with a precision that cannot be reached by
other current means, up to the bridging of two electrodes of less
than 5 m in diameter and over 50 m in length by a single
use of
electropolymerization mechanism reaches
precision in the sense that fibers can only nucleate from the anode, orientation on nano- and micrometer scales, is at the moment
a
single electrical stimulus, the supramolecular
nanowire. Such
a
precise control in every aspect of
a
much higher
supramolecular polymerization, including localization and
opening new possibilities to grow selectively single wires between
two-point electrodes (as in Figure 3d).
quite unique in the literature. Other potential implementations
resulting from these experiments include for instance: (i) spatial
control over self-assembly processes in various optoelectronic
devices requiring efficient charge transport and ranging from
sensors to solar cells,[24,25] (ii) use of waste-free electrochemistry
tools to control (living) supramolecular polymerization or to create
out-of-equilibrium redox environments for self-organized
systems,[26] and (iii) design of 3D electrical wiring in organogels.
Acknowledgements
The research leading to these results has received funding from
the European Research Council under the European
Community's Seventh Framework Program (FP7/2007-2013) /
ERC Starting Grant agreement n°257099 (N.G.), the European
Union (FP7/2007-2013, ITN Read), the Agence Nationale de la
Recherche (STANWs ANR-11-EMMA-0009) and the international
center for Frontier Research in Chemistry (icFRC). We also thank
the Centre National de la Recherche Scientifique (CNRS), the
COST action (CM 1304), the Laboratory of Excellence for
Complex System Chemistry (LabEx CSC), the University of
Strasbourg (UdS), and the Institut Universitaire de France (IUF).
Part of this work was performed within the framework of the IRTG
“Soft Matter Science: Concepts for the Design of Functional
Materials” (M.G., E. M. and N.G.). We acknowledge the Electron
Microscopy Facility of the Institut Charles Sadron. We finally thank
André Schroeder for help with optical microscopy.
Figure 3. (a) SEM image of an IDE prepared with a 2 mg/mL solution of 1 in the
presence of an applied field of 1.25 x 107 V∙m-1 and highlighting the nucleation
taking place from the anode only; (b) plot of the order parameter (S) as a
function of the field strength (dots: [1] = 5 mg/mL; triangle: [1] = 2 mg/mL), the
error bars are calculated from four different regions of the IDEs; (c) AFM image
of an IDE prepared with a 2 mg/mL solution of 1 in the presence of an applied
field of 1.25 x 107 V∙m-1 and highlighting the formation of thin fibers with
nucleation taking place from the anode only; (d) POM image of a microelectrode
array showing a single wire grown from the anode to the cathode, parallel to the
electric field (white arrow) and over a distance of 50 μm.
Conflict of interest
Finally, from a functional point of view, the mobility of charge
carriers within the supramolecular nanowires formed by this
technique in interdigitated electrodes was derived from the
current vs voltage measurement and by using the space charge
limiting approximation[21] (which is justified by the low
concentration of ions introduced in the system) (section S14). By
assuming the number of wires in the electrodes, and by assuming
all of them being connected, we can estimate a minimum value
as high as 0.56 cm2∙V-1∙s-1, close to the theoretical prediction
published in the literature.[22]
In conclusion, we have described the first example of what can be
defined as a “supramolecular electropolymerization” process. It
represents a new tool of fundamental and practical interest for
supramolecular chemistry in general. To this end, we have used
triarylamines but one can imagine to extend the concept to other
molecules with red-ox functionalities and capable of forming
supramolecular polymers or self-assemblies involving charge
transfer complexes.[23] In addition, we have shown that the
mechanism involved can be used to gain control over the precise
The authors declare no conflict of interest.
Keywords: Supramolecular polymers • Electrochemistry • Smart
materials • Nanowires • Supramolecular electronics
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Entry for the Table of Contents
COMMUNICATION
Thomas K. Ellis, Melodie Galerne,
Joseph J. Armao IV, Artem Osypenko,
David Martel, Mounir Maaloum, Gad
Fuks, Emilie Moulin, Odile Gavat, and
Nicolas Giuseppone*
The direct electrochemical oxidation of
triarylamines at anodes triggers their
nucleation and growth into
supramolecular polymers. This
mechanism can be defined as a
supramolecular electropolymerization
process. It is used to grow and
Page No. – Page No.
Supramolecular
Electropolymerization
precisely address single nanowires
over a distance of 50 m between two
electrodes in a DC electric field.
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