Fabrication of Neutral Supramolecular Polymeric Films via Post-electropolymerization of Discrete Metallacycles

Article abstract of DOI:10.1002/cjoc.201700610

Self-assembly post-modification has proven to be an efficient strategy to build higher-order supramolecular architectures and functional materials. In this study, we successfully realized the construction of a new family of neutral supramolecular polymeric films containing well-defined metallacycles as the main scaffolds through combination of coordination-driven self-assembly with post-electropolymerization. The obtained neutral polymeric materials were fully characterized by the cyclic voltammogram (CV), SEM, and TEM. The thickness of the films was able to be well regulated by the number of scanning cycles. Moreover, we found that the shape of the metallacycles and the number of triphenylamine moieties played important roles in the formation of the final polymer films. We believe that the introduction of the neutral metallacycles into the final polymer structures not only enriches the library of supramolecular polymeric films but also provides a new platform to study neutral molecule detection, separation, and capture.

Full text of DOI:10.1002/cjoc.201700610

Fabrication of Neutral Supramolecular Polymeric Films via
Post-electropolymerization of Discrete Metallacycles
Guang-Qiang Yin, Li-Jun Chen, Cui-Hong Wang*, Hai-Bo Yang*
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engi-
neering, East China Normal University, 3663 North Zhongshan Road, Shanghai 200062, P. R. China
Self-assembly post-modification has proven to be an efficient strategy to build higher-order supramolecular ar-
chitectures and functional materials. In this study, we successfully realized the construction of a new family of neutral
supramolecular polymeric films containing well-defined metallacycles as the main scaffolds through combination of
coordination-driven self-assembly with post-electropolymerization. The obtained neutral polymeric materials were
fully characterized by the cyclic voltammogram (CV), SEM, and TEM. The thickness of the films was able to be well
regulated by the number of scanning cycles. Moreover, we found that the shape of the metallacycles and the number
of triphenylamine moieties played important roles in the formation of the final polymer films. We believe that the
introduction of the neutral metallacycles into the final polymer structures not only enriches the library of supramo-
lecular polymeric films but also provides a new platform to study neutral molecule detection, separation, and capture.
Keywords coordination-driven self-assembly, post-electropolymerization, neutral metallacycle, triphenylamine, su-
pramolecular polymeric films
Introduction
Electrochemical Oxidation.
Coordination-driven self-assembly has evolved to be a
powerful bottom-up approach to construct discrete supra-
molecular architectures with well-defined shapes and
sizes including two-dimensional (2-D) polygons and
three-dimensional (3-D) polyhedra.1 These discrete
metallosupramolecular architectures are of particular in-
terest not only because of their aesthetically pleasing
structures but also due to their wide applications in many
areas such as host−guest chemistry, catalysis, bioengi-
neering, etc.2 Notably, inspired by the fact that biological
systems in nature frequently employ self-assembly post-
modification strategy to tune the structures and function-
alities of biological scaffolds3, recent research effort has
been devoted to construction of functionalized metallo-
supramolecular complexes by employing self-assembly
post-modification strategy4. Generally, post-modification
of discrete metallacycles or metallacages can be obtained
through combining supramolecular self-assembly with
facile covalent reaction or polymerization. For example,
Nitschke et al. have successfully employed imine ex-
change reaction to realize multistep transformation of
their metallacages guided by the Hammett equation.5
Moreover, we have also previously reported the construc-
tion of smart supramolecular polymeric hydrogels via
self-assembly post-polymerization of discrete organo-
platinum(II) metallacycles.6 However, it is still very chal-
lenging to realize the construction of well-controlled pol-
ymeric films though post-modification of discrete supra-
molecular architectures due to the lack of suitable organ-
ometallic scaffolds with proper covalent reaction sites.
As an electrochemically active moiety, triphenyla-
mine (TPA) has proven to be dimerized to form tetra-
phenylbenzidine (TPB) through electrochemical oxida-
tion (scheme 1).7 Thus, TPA derivatives have been suc-
cessfully employed as a handle for electropolymerization
to form ordered films such as conjugated donor−acceptor
polymer films.8 Previously, we reported the fabrication of
a series of well structurally defined polymeric films from
TPA functionalized metallacycles by means of post-elec-
tropolymerization.9 However, the obtained polymeric
films contained multiple positive charges around the pore
channel due to the formation of nitrogen-to-metal coor-
dination bonds in metallacycles skeleton, thus limiting
their further application in detection or capture of neutral
molecules. The construction of new polymeric film with
neutral metallacycles as main scaffold through post-
polymerization has not been explored yet. It should be
noted that there is another established way to construct
metallacycles based on oxygen-to-platinum coordina-
tion-driven self-assembly that resulted in the formation
of neutral supramolecular assemblies. Compared to the
charged metallacycles, neutral metallacycles have proven
to have higher solubility in organic solvents and exhibit
better encapsulation ability for neutral organic guests.10
Thus, we envision that self-assembly post-electropoly-
merization of neutral metallacycles may lead to the gen-
eration of a new family of neutral polymeric film and pro-
Scheme 1 Dimerization of Triphenylamine (TPA) through
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been through the copyediting, typesetting, pagination and proofreading process, which
may lead to differences between this version and the Version of Record. Please cite this
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vide a better understanding of the influence to electropol-
ymerization caused by the structural factors.
centrifuged. The precipitate was then washed with the
distilled water for three times and dried under vacuum at
room temperature to afford rhomboid M2 as a white solid
(29.3 mg, 95%). 1H NMR (400 MHz, CD2Cl2): δ 8.72 (s,
2H), 8.60 (s, 1H), 8.26 (d, J = 1.4 Hz, 2H), 7.76 (d, J =
8.0 Hz, 2H), 7.46 (s, 2H), 7.42 (d, J = 8.5 Hz, 4H), 7.31
(t, J = 7.9 Hz, 4H), 7.13 (d, J = 7.6 Hz, 4H), 7.09 (t, J =
7.4 Hz, 2H), 7.02 (d, J = 8.6 Hz, 2H), 1.56 (dd, J = 7.2,
3.6 Hz, 24H), 1.22 – 1.16 (m, 36H). 31P NMR (162 MHz,
CD2Cl2): δ 16.96 (s, 1JPt-P = 2885.22 Hz).
Herein, we designed and synthesized a new 120o TPA
substituted dicarboxylate donor ligand and the comple-
mentary 120o TPA functionalized di-Pt(II) acceptor
building blocks, from which two novel neutral multi-TPA
functionalized 2-D metallacycles with different shape
and size were successfully obtained via the formation of
oxygen-to-platinum coordination bonds. Subsequent
post-electropolymerization of those two neutral multi-
TPA containing metallacycles allowed for fabrication of
a new type of neutral polymeric film with well-controlled
cavity sizes and thickness, which may have potential ap-
plication in neutral molecule detection, separation, and
capture.
General Procedure for Post-Electropolymerization
Post-electropolymerization of the neutral metallacy-
cles M1 or M2 (0.2 mM) was carried out by taking cyclic
voltammetric method (+0.4 ~ +1.5 V) in CH2Cl2 with n-
Bu4NPF6 (0.1 M) as the supporting electrolyte. Cyclic
voltammograms of the polymers were obtained on a Pt
working electrode with a Pt wire as the counter electrode
and an Ag/AgCl (saturated) electrode as the reference
electrode.
Experimental Section
All reagents were analytical purity and used without
further purification. L1 was synthesized according to the
literature procedures.9 Metallacycles M1 and M2 were
dissolved in CD2Cl2 for 1H and 31P{1H} NMR analysis.
Results and discussion
Preparation of Hexagon M1.
Scheme 2 Synthetic Route of 120o TPA Donor L2.
To a mixture of L1 (29.26 mg, 0.021 mmol) and L2
(10.00 mg, 0.021 mmol) in a 10 dram vial, the mixture
solvents （3.0 mL）of acetone and H2O (v/v, 5/1) was
added. Then the mixture was stirred at 50 ºC for 8 h. After
being cooled down to room temperature, acetone was re-
moved by nitrogen gas flow. The suspension was then
centrifuged. The precipitate was washed with distilled
water for three times and then dried under vacuum at
room temperature to afford hexagon M1 as a white solid
(33.0 mg, 93%). 1H NMR (400 MHz, CD2Cl2): δ 8.36 (s,
1H), 8.07 (s, 2H), 7.32 – 7.27 (m, 4H), 7.21 (t, J = 7.4 Hz,
8H), 7.01 (dd, J = 17.5, 8.8 Hz, 15H), 6.91 (d, J = 7.7 Hz,
4H), 1.87 (d, J = 3.1 Hz, 24H), 1.18 – 1.11 (m, 36H). 31P
N
I
Pd(PPh3)4, CuI
N
+
THF, Et3N
92%
H3COOC
COOCH3
9
H3COOC
COOCH3
3
10
N
N
1.NaOH, THF, MeOH
2.HCl
NaHCO3
THF
95%
85%
1
NMR (162 MHz, CD2Cl2): δ 18.75 (s, JPt-P = 2522.34
Hz).
HOOC
COOH
NaOOC
COONa
11
L2
Preparation of Rhomboid M2.
According to the “directional bonding” model and the
“symmetry interaction” model11, the ligands that incor-
porate a 120o angle between the active coordination sites
can interact with the suitable complementary ditopic mo-
lecular modules to yield molecular rhomboids or hexa-
gons. Thus, 120o TPA functionalized
To a mixture of L2 (10.00 mg, 0.021 mmol) and 12
(24.41 mg, 0.021 mmol) in a 10 dram vial, the mixture
solvents （2.4 mL）of acetone and H2O (v/v, 5/1) was
added. Then the mixture was stirred at 50 ºC for 8 h. After
being cooled down to the room temperature, acetone was
removed by nitrogen gas flow. The suspension was then
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Scheme 3 Graphical Representation of Self-assembly of Neutral Metallacycles M1 and M2.
di-Pt(II) acceptors building block L1 and 120o TPA sub-
stituted dicarboxylate donor ligand L2 were designed and
synthesized. For instance, L2 was readily synthesized by
several steps of a Pd-catalyzed Sonogashira coupling re-
action in high yield as shown in Schemes 2. All the new
compounds were characterized by multiple nuclear NMR
spectroscopies (1H, 31P{1H}, and 13C) (Figs. S1-S12).
With these TPA decorated building blocks in hand, the
construction of neutral TPA modified metallacycles were
then carried out. The hexagonal metallacycle M1 was se-
lected as a representative to illustrate the formation pro-
cess. Stirring a mixture of L1 and L2 in an exact stoichi-
ometric ratio (1:1) in acetone/H2O (v/v, 5/1) mixed sol-
vent at 50 ºC for 8 h led to the formation of hexagon M1
without the need for further purification. Similarly, self-
assembly of L2 assembled with an equimolar amount of
12 resulted in the formation of rhomboid M2 in almost
quantitative yield.
the increase of electron density. The sharp NMR (1H and
31P{1H}) signals along with the good solubility strongly
demonstrated that a set of discrete, highly symmetric
metallacycles were assembled rather than the random lin-
ear supramolecular polymers.
The formation of the discrete, neutral macrocyclic
structures with high symmetry was further evidenced by
1H and 31P{1H} NMR spectroscopy (Figs. 1, 2, and S6-
S12). For example, the 31P{1H} NMR spectrum of hexa-
gon M1 (Fig. 1b) presented a sharp singlet (ca. 16.96 ppm)
shifted towards upfield compared with the starting plati-
num acceptor L1 (Fig. 1a) by approximately 2.10 ppm
due to the electron back-donation from the platinum at-
Fig. 1 The 31P NMR spectra (162 MHz, CD2Cl2, 298 K) of (a) lig-
and L1 and (b) metallacycle M1.
1
oms. Moreover, in the H NMR spectrum of M1 (Figs.
2b and S7), all signals of protons of L1 (Figs. 2c) exhib-
ited nearly unchanged. While the protons that corre-
sponded to L2 (Figs. 2a) showed significantly downfield
shifts, which is consistent with the coordination of oxy-
gen atoms to platinum centers. For instance, the signals
of H1 and H2 protons of L2 shifted towards downfield by
0.23 and 0.18 ppm, respectively. Multinuclear NMR (1H
and 31P{1H}) analysis of M2 (Figs. S9-S12) displayed
very similar sharp and order characteristics to M1. For
example, as shown in the Fig. S10, all signals of protons
of L2 shifted towards downfield (Δδ[H1] = 0.40 ppm;
Δδ[H2] = 0.76 ppm) due to the loss of electron density
upon coordination of the oxygen atom with platinum
metal centers. The peaks assigned to Ha and Hb protons of
ligand 12 shifted considerably into the upfield region by
0.24 ppm and 0.18 ppm, respectively, associating with
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Fig. 2 Partial 1H NMR spectra (400 MHz, in CD2Cl2, 298 K) of (a)
donor L2, and (b) metallacycle M1, (c) acceptor L1.
Fig. 3 The X-ray crystal structures of macrocycle M2 (a) top view,
(b) side view. A molecule of dichloromethane is encapsulated.
With the considerable efforts, the single crystal of
rhomboid M2 was obtained by slow diffusion of ether
into a solution of M2 (10.0 mM) in dichloromethane at
ambient temperature for two weeks. The crystal structure
of M2 (Fig. 3) clearly demonstrated the successful [2+2]
self-assembly of L2 and 12 with a rhombic structure. In
the crystal structure of M2, the coordinated angle of L2
is about 123°, which was extremely close to the ideal
value 120°. The distance of TPA units is approximately
3.4 nm. Interestingly, as shown in Fig. 3b, the side view
of the crystal displayed an “S” shape with four PEt3
groups being perpendicular to the plane of the metallacy-
cle.
All above-mentioned data strongly indicated that the
neutral metallacycles decorated with different numbered
TPA moieties can be easily prepared through the for-
mation of Pt-O bonds via coordination-driven self-as-
sembly. This strategy avoided the time-consuming proce-
dures and lower yields often encountered in covalent syn-
thetic protocols. More importantly, the presence of the
regular cavity core with different shape and size offered
the possibility of the formation of well-controlled porous
structures.
With the aim to obtain neutral polymeric film, the
subsequent cyclic voltammetry (CV) electropolymeriza-
tion of these two neutral multi-TPA metallacycles M1
and M2 was performed in a dichloromethane solution
containing 0.1 M n-Bu4NClO4 as the supporting electro-
lyte at a ~7.0 mm2 Pt disk electrode. As shown in Fig. 4a
and Fig. 4c, the CV of M1 and M2 with the repeatedly
scanning the potential from +0.4 to +1.5 V vs Ag/AgCl
for 15 cycles was performed. The anodic/catholic peak
current ratios of ia/ic ≈ 1 was observed due to the one elec-
tron oxidation of the TPA groups. In addition, during CV
experiment, the gradual increase of current indicated that
the electropolymerization of M1 or M2 proceeded
smoothly and successfully,8a resulting in the deposition
of macroscopic polymer films on the electrode surface.
The mechanism of TPA polymerization is believed to
possess a highly unstable monocation radical intermedi-
ate.8c,d Both peak potential shifts along with the emer-
gence of a new shoulder redox peak was attributed to the
All attempts to characterize the neutral metallacycles
M1 and M2 by using ESI-MS or MALDI-TOF-MS have
so far proven unsuccessful which might be caused by the
labile interaction of platinum-oxygen coordination as
well as the relatively large molecular weight of both
metallacycles. Notably, the X-ray crystallographic analy-
sis of rhomboid M2 clearly demonstrated the existence
of neutral rhomboidal metallacycle. In addition, accord-
ing to the “directional bonding” model and the “sym-
metry interaction” model6a,d,j,k,p, the combination of two
complementary ditopic building blocks A2 and X2, each
incorporating 120° angels between their coordination
sites, allows for the formation of hexagonal structures of
type A2 X2 . It should be noted that it is not possible to
3
3
form polygons with an odd number of sides (i.e. triangle,
pentagon, heptagon, etc.) by combining 120° donors with
120° acceptors since they would require the direct con-
nection of either two acceptor or two donor moieties. The
successful formation of neutral dendritic hexagons via
oxygen-to-platinum coordination has been realized pre-
viously through the similar strategy10d. Thus the sharp 1H
NMP signals as well as the singularity of each 31P NMR
signal ensures that only [3+3] hexagon M1 was formed
in this study.
N
0/+ process of the newly generated tetraphenylbenzidine
unit as a result of the oxidative coupling between the di-
phenylaminegroups of M1 or M2.
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synthetic methodology is rather straightforward with
high-yield as well as without further purification process.
More importantly, the neutral polymeric films containing
the uncharged metallacycles were successfully prepared
via post-electropolymerization. The further investigation
revealed that thickness of the obtained polymer films was
readily controlled by the number of scan cycles. Moreo-
ver, the poly-M1 exhibited well-defined and compact
polymeric sheet-like film instead of fiber-like morphol-
ogy of the poly-M2. To the best of our knowledge, this
study provides the first successful example of neutral pol-
ymeric films containing the well-defined metallacycles
as the main scaffolds through post-electropolymerization.
The investigation on the future application of these neu-
tral polymeric films like the selective molecular transfor-
mation is undergoing in our lab.
Fig. 4 Electropolymerization of M1 (a) and M2 (c) (0.2 mM in
CH2Cl2) at a Pt disc electrode (d = 2 mm). Film thickness vs scan
cycles for M1 (b) and M2 (d).
Furthermore, the thickness of films was estimated by
scanning electronic microscopy (SEM) images. Intri-
guingly, the thickness of poly-M1 (Figs. 4b, S13) or poly-
M2 (Figs. 4d, S14) were increased steadily as the number
of scan increased. This finding indicated that the thick-
ness of the obtained film could be readily regulated. For
example, the poly-M1 films with different thickness such
as 15, 30, 50, 70 nm were achieved with 1, 2, 4, 6 scan
cycles, respectively. By this means, a series of neutral
polymeric films with certain thickness could be easily
prepared.
With the aim to probe the film morphology, the elec-
tropolymerization of neutral metallacycles M1 and M2
was successfully performed on indium tin oxide (ITO)
glass electrode to prepare poly-M1 and poly-M2 films in
situ. Scanning electronic microscopy (SEM) and trans-
mission electron microscopy (TEM) are highly reliable
tools to provide evidence for the morphology of the films.
The SEM analysis of poly-M1/ITO (Fig. 5a) as well as
poly-M2/ITO (Fig. 5e) indicated that the poly-M1 and
poly-M2 films were adhered tightly to the ITO substrate.
Apparently, the morphology of poly-M1 films was much
more smooth and compact than poly-M2 film. Notably,
as shown in the TEM, poly-M1 film (Figs. 5c and 5d)
displayed a sheet like morphology rather than linear fiber
as poly-M2 film (Figs. 5g and 5h). Actually, the results
of SEM and TEM of poly-M1 and poly-M2 films were
consistent with structures of neutral metallacycles M1
and M2 as linear and 120o orientation of TPA moieties,
respectively. This finding indicated that the structural ef-
fect of the metallacycle played an important role in the
formation of the final polymeric film materials.
Fig. 5 Side view (a) and top view (b) of representative SEM pic-
tures of poly-M1/ITO film. TEM micrographs of thin film frag-
ment at low magnification (c) and the enlarged area (d). Side view
(e) and top view (f) of representative SEM pictures of poly-
M2/ITO film. TEM micrographs of thin film fragment at low mag-
nification (g) and the enlarged area (h).
Conclusions
In summary, we designed and synthesized a new se-
ries of TPA substituted dicarboxylate donor and comple-
mentary 120o TPA functionalized di-Pt(II) acceptor
building blocks. Through the formation of Pt–O bonds
via coordination-driven self-assembly, the successful
fabricatation of neutral multi-TPA functionalized metal-
lacycles with different shape and size were obtained. The
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Acknowledgement
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Fabrication of Neutral Poly-
meric Films Containing Well-de-
fined Metallacycles via Post-
Electropolymerization.
Guang-Qiang Yin, Li-Jun Chen,
Cui-Hong Wang*, Hai-Bo Yang*
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