Vertical Step-Growth Polymerization Driven by Electrochemical Stimuli from an Electrode

Article abstract of DOI:10.1002/anie.201809567

We present herein the vertical step-growth polymerization of a monomer A-B through individual A–A or B–B coupling driven by electrochemical switching of positive and negative bias on a self-assembled A or B electrode. The monomer Ru^II(bda)AB (bda=2,2′-bipyridine-6,6′-dicarboxylate), in which A and B are pyridine moieties with pendant carbazolyl and vinyl groups, could be dimerized at oxidative (ca. 1.0 V vs. Ag/Ag⁺) or reductive potential (ca. ?1.8 V) to give a self-assembled Ru^II(bda)PA or Ru^II(bda)PB monolayer (P=pyridine with a pendant phosphonic acid) on ITO glass. This polymerization enabled the sequence- and topology-controlled synthesis of surface-confined molecular wires with single-molecule precision on an electrode. The electrocatalytic performance of the vertically orientated molecular wires for water oxidation increased with increasing molecular length and exceeded that of both the self-assembled monolayer and a randomly electropolymerized film, which have previously been studied as typical models.

Full text of DOI:10.1002/anie.201809567

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Accepted Article
Title: Vertical Step-Growth Polymerization Driven by Electrochemical
Stimuli from Electrode
Authors: Jian Zhang, Jia Du, Jinxin Wang, Yangfang Wang, Chang
Wei, and Mao Li
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201809567
Angew. Chem. 10.1002/ange.201809567
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10.1002/anie.201809567
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Vertical Step-Growth Polymerization Driven by Electrochemical
Stimuli from Electrode
Jian Zhang,[a],[b] Jia Du,[a] Jinxin Wang,[a],[c] Yanfang Wang,[a] Chang Wei,[a],[c] and Mao Li*[a],[b]
Dedication ((optional))
Abstract: We presented here that vertical step-growth
polymerization of monomer A-B via individual A-A or B-B coupling
driven by electrochemically switching positive and negative bias on
wires on substrates from self-coupling reactions, and (2) iterative
dipping and rising processes are hampered by time consuming
operation and the use of a large amount of solvent. Rapid and
self-assembled
A
or
B
electrode. In particular, monomer is
economical
one-pot
covalent
assembly
with
tuning
Ru(II)(bda)AB (bda = 2,2′-bipyridine-6,6′-dicarboxylate), where A and
B are pyridines with pendant carbazolyl and vinyl, which can be
dimerized at oxidative potential (ca. 1.0 V vs. Ag/Ag+) and reductive
potential (ca. -1.8 V), respectively. Self-assembled monolayers on
ITO glass are Ru(II)(bda)PA or Ru(II)(bda)PB (P = pyridine with
pendant phosphonic acid). This well-controlled polymerization allows
us to synthesize surface confined molecular wire in single molecule
precision on electrode with sequence- and topology-controlled
possibility. The electrocatalytic performance based on water
oxidation of vertically orientated molecular wires rises up with
increasing molecular length, and oversteps those of both self-
assembled monolayer and randomly electropolymerized film, which
physicochemical properties becomes highly desirable for
practical applications.
As a simple and low cost programmable technique, the
electrochemical oxidation and reduction have long been
individually used to fabricate conducting polymers[11] without
controllable sequence and degree of polymerization because
two oxidative or reductive sites[12-14] of monomer can be
simultaneously activated. Therefore, single oxidative reactive
site and single reductive reactive site coexsisting in an identical
molecule should enable us to one by one control the single
molecular assembly via step growth polymerization by
alternatively switching positive and negative bias. In this paper,
were generally studied as two typical models by most of researchers. we have firstly designed Ru complex with both electrooxidative
With function-tuning ability and rapid fabrication, it is highly
anticipated that this polymerization and one-pot single molecule
controlled assembly has highly promising potentials for practical
applications with expectably superior performances.
(carbazolyl) and electroreductive (vinyl) reaction units for one-
pot single molecule controlled assembly on electrode (Scheme
1a). This vertical step growth polymerization has successfully
prevented the self-coupling within SAM and between vertically
molecular wires on electrode, and allows single molecule
controlled assembly to be processed in one-pot without moving
or changing experimental gears.
Controlled covalent formation of organized molecular building
blocks based on solution deposition is of great importance and
challenge for next generation applications such as electronics,[1]
sensors,[2] catalysis,[3] and bio-relatives.[4] By now, self-
assembled monolayers (SAMs) and thin films are well known as
two successful camps to have been considering for practical
applications.[5] Though molecules can serve in theory as an
ultimate functional building block,[6] there is lack of truly number
and sequence controlled one by one single molecular assembly
on substrates as well as solid phase peptide synthesis,[7] which
is key to broaden the molecular scale applications. Molecular
assemblies based on non-covalent step growth polymerizations
such as metal coordination,[8] hydrogen bond[9] and host-guest
recognition[10] have great potential in precisely single molecule
controlled assembly. However, there are remaining tough
challenges including that (1) how to prevent vertically molecular
Scheme 1. Step-growth polymerization driven by electrochemically switching
oxidative and reductive potentials on electrode pre-modified with CzP.
[a]
J. Zhang, J. Du, J. Wang, Y. Wang, C. Wei, Prof. Dr. M. Li
State Key Laboratory of Polymer Physics and Chemistry
Changchun Institute of Applied Chemistry (CIAC)
Changchun 130022, China
As shown in Scheme 1, monomer RuCzV possessing pendant
carbazolyl and vinyl, and self-assembled monolayer CzP
possessing pendant carbazolyl and phosphonic acid were
designed and inspired by well-known Ru(II)(bda) (bda = 2,2′-
bipyridine-6,6′-dicarboxylate) unit used for highly active water
oxidation catalysts (WOCs).[15] Electrochemically reductive
coupling of vinyls[16] and oxidative coupling of carbazolyls,[17,18]
take place at -1.8 V and 1.0 V vs. Ag/Ag+, respectively, and
produce saturated bond (Scheme 1b) and 3,3′-bicarbazole
E-mail: limao@ciac.ac.cn
J. Zhang, Prof. Dr. M. Li
University of the Chinese Academy of Sciences
Beijing 100049, China
J. Wang, C. Wei
[b]
[c]
University of Science and Technology of China
Hefei 230026, China
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.201809567
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formations (scheme 1c). In order to achieve the vertical
molecular wire on substrate, the design of self-assembly
molecule and Ru complex was considered to that how to avoid
the self-coupling reactions of carbazolyls within SAM on
electrode.[19] Notably, self-assembled 9-octylcarbazole was not
utilized for pre-modification of electrode due to self-coupling of
carbazoles within SAM, where redox peaks of 3,3-bicarbazole
was observed in cyclic voltammetry (CV) (Figure S1). In the
case of CzP for SAM, Ru2+ and 2,2′-bipyridine units have lower
oxidative and reductive potentials (Figure S2-6), and they should
be preferentially oxidized or reduced as positively or negatively
charged state, leading to same charge repulsion within SAM and
between vertical molecular wires for probably restrained self-
couplings between neighbor molecules.
molecular wire after treatment of HF, but no evidence was
obtained probably due to detection limit for trace molecules. CVs
were measured in aqueous solution instead of acetonitrile
because of better observation of redox peaks. After n rises up to
9, the further polymerization is going to be difficult (Figure 1a)
probably due to that the length of CzP(Ru)9 has reached the
width of electric double layer, which is generally considered to
be 20 nm as maximum. As auxiliary evidences, CzP(Ru)9 in
solid state has a thickness of ~23 nm (Figure 2b,c), which is in
good agreement with theoretical value of 25.8 nm in extended
state (Figure 2d). In contrast to linear molecular wire (Figure 2a),
the molecular wire VP(Ru)n (VP = Ru complex possessing
pyridines with pendant vinyl and phosphonic acid) with different
sequence can be obtained on self-assembled VP on ITO
electrode (Figure 1b,1d, 2e, S10). The cross-point in Figure 1b
is considered to be due to the random measurement points of
UV-vis spectra, while good linear relationships in Figure 1d is
obtained from statistical measurement of entire electrode.
Furthermore, topologically controlled non-linear molecular wires
could be possible if both C(3)-C(3’) and C(6)-C(6’) couplings of
carbazole were simultaneously activated at high oxidative
potential of ≥1.2 V.[18]
Figure 1. UV-vis spectra (a), absorbance at 500 nm (b), CVs (c) and current
intensity of redox peaks of Ru2+/3+ (d) of CzP(Ru)n or/and VP(Ru)n.
During alternatively switching positive and negative potentials
of self-assembled ITO/CzP electrode in 0.5 mM RuCzV
acetonitrile solution, the couplings of carbazolyl and vinyl of
RuCzV in solution with carbazolyl and vinyl of ITO/CzP electrode
were performed under nitrogen environment at dynamic
potentials (E = -0.3 V~1.0 V, 20 mV/s, 1 cycle, Figure S7a) and
constant potential (E = -1.8 V, 100 s, Figure S7b), respectively,
considered based on dynamic controllability and low reactivity of
vinyl in Ru complex.[14b,d] The polymerization of molecular wire
CzP(Ru)n continues in single molecular precision (Scheme 1d)
and it can be demonstrated by single molecular dependent
absorbance (the metal to ligand charge transfer band at ~510
Figure 2. (a) CzP(Ru)n synthesized by step polymerization. (b) Thicknesses
obtained from AFM image (b), SEM image (c), and theoretical value (d). (e)
VP(Ru)n with alternative sequence by step polymerization.
nm, Figure S8) and electrochemical redox peaks (Ru2+/3+, E1/2
=
0.43 V vs. Ag/AgCl). As the number of Ru units increases
referred to SAM (CzP(Ru)n, n = 0), the absorbance and current
intensity of CzP(Ru)n regularly grow and exhibit good linear
relationship with switching times of alternative potentials (Figure
1,2a). Additionally, the intermittent growth of peak at 700 nm can
be ascribed to emergence of more Ru3+ species through
electrochemical oxidation (Figure S9) according to previous
reports.[20] Mass spectrometries were utilized for analyzing the
Figure 3. Illustrations and AFM images of surface confined CzP(Ru)n (a) and
random poly(RuCz2)m film (b) with similar molecular surface coverage of Ru
units controlled by CV cycles.
CzP(Ru)n in solid state show surface confined
nanostructures with tiny change of RMS (Figure 3a, Figure
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S13a), in contrast to non-specific random and uniform
poly(RuCz2)m (RuCz2 = Ru(II)(bda) complex possessing two
pyridines with pendant carbazolyls) film (Figure 3b, Figure S13b)
with similar surface coverage of Ru units (Figure S11, S12).
Furthermore, CzP(Ru)n (n = 0 and 9) with this specially
nanostructural orientation was estimated by electrochemically
active surface area (ECSA)[21] and electrochemical kinetics at
electrode-media interfaces. According to typical scan rate
dependent CV traces (Figure 4a, S14), the capacitive current at
0.05 V is plotted as a function of scan rate to extract double
electrocatalytic water oxidation inspired by well-known Ru
complex.[15] With length increase from n = 0 to n = 9 of CzP(Ru)n,
the catalytic currents density of water oxidation, progressively
rises up to 66.2 μA cm-2 in Figure 5a (surface coverage is
13.2×10-10 mol cm-2), while poly(RuCz2)m film with similar surface
coverage (13.8×10-10 mol cm-2) shows a current density of 35.5
μA cm-2, indicating CzP(Ru)9 is superior to SAM and
poly(RuCz2)m film for electrocatalytic water oxidation. The
oxidation peaks of Ru2+/Ru3+ and Ru3+/Ru4+ of CzP(Ru)n appear
at 0.77 V and 1.40 V (vs. NHE) respectively,[23] and gradually
layer capacitance (CDL) from the slopes of fitting lines (Figure 4b). increase as build-up of CzP(Ru)n. The oxidation peak of 3,3-
CDL of CzP(Ru)9 is calculated to be 0.19 mF, which is
significantly ~5 times higher than those of CzP and poly(RuCz2)m
film with a value of 0.039 mF. In equation ECSA = CDL/Cs, Cs are
similar if CzP(Ru)9 and poly(RuCz2)m films were considered to
possess same Ru units, which can be confirmed by redox
charges of Ru units (Figure S15). Thus, CzP(Ru)9 should have
superior large ECSA to poly(RuCz2)m film. Additionally, the
electrode kinetics was evaluated by electrochemical impedance
spectroscopy (EIS) that CzP(Ru)9 and CzP have almost identical
diffusion impedance, which is much higher than those of
poly(RuCz2)m film with mostly resistive behavior (Figure 4c),
indicating that the surface-confined assemblies without altering
interfacial electronic property of their original SAM template.
CzP(Ru)9 and CzP have the charge transfer dominating region
as semicircles at high frequency with resistances of 52.9 Ω and
58.9 Ω, respectively, while poly(RuCz2)m film has a relatively
high resistance of 67.1 Ω, probably owing to the facilitating
funneling or hopping process of electron transfer between
oriented molecular wires[22] compared to compact and uniform
poly(RuCz2)m film (Figure 4d).
bicarbazole should be at 1.20 V (vs. NHE). As for poly(RuCz2)m
film, the oxidative potential of Ru2+ slightly increases to 0.84 V
and has a broader peak width, indicating sluggish electron
transfer, which is in good agreements with Figure 4c-d. In
controlled potential electrolysis (Figure 5b), CzP(Ru)9 and
poly(RuCz2)m show negligible current decline during
1 h
electrolysis, indicating the robust catalysts loading without
desorption or inactivation occurs. The catalytic current density of
41.4 μA cm-2 for molecular wire CzP(Ru)9 also significantly
surpass over that of poly(RuCz2)m film with a value of 26.1 μA
cm-2. Molecular wire CzP(Ru)n not only offers tunable
electrocatalytic properties based molecular scale, also exhibits
superior electrocatalytic performance to general SAM and
electropolymerized film, making it promising candidate for single
molecule controlled catalysts loading.
Figure 5. (a) Linear sweep voltammetry of bare ITO, CzP(Ru)n, poly(RuCz2)m,
and CzP(Ru)x on ITO at a scan rate of 20 mV/s. (b) controlled potential
electrolysis at 1.7 V (vs. NHE) in 0.1 M HClO4 aqueous solution, and (c)
Absorption spectra of CzP, CzP(Ru)9 and CzP(Ru)x prepared by switching
constant potentials between 1.0 V and -1.8 V (d).
Figure 4. (a) CVs of CzP(Ru)9 in non-Faradaic region at scan rates of 5, 10,
25, 50, 100, 200, 400, 600 and 800 mV/s, and (b) current intensity of redox
peaks at 0.05 V as a function of scan rates. (c) Nyquist plots of CzP, CzP(Ru)9,
poly(RuCz2)m, and (d) their magnifications of high-frequency region with
illustration of equivalent circuit.
To further elucidate the advantage of electrochemical route
in high speed assembly, in 10 min, the molecular wire CzP(Ru)x
with a surface coverage of 7.85×10-10 mol cm-2, which is ~70%
of CzP(Ru)9, was fabricated by programmable switching
constant potentials between 1.0 V and -1.8 V (Figure 5c-d).
Though this rapid mode does not provide theoretically values in
absorbance, linear sweep voltammetry and controlled potential
electrolysis (Figure 5a-c) probably due to sluggish molecular
immigrations at interface of electrode, it does also show
With superiorities of high ECSA, abundant active sites and
fast electron transfer kinetics of CzP(Ru)n at interface of
electrode, one attractive potential application lies in
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Nishihara, Chem. Soc. Rev. 2015, 44, 7698; d) E. Katz, G. Scheller, T.
M. Putvinski, M. L. Schilling, W. L. Wilson, C. E. D. Chidsey, Science
1991, 254, 1485; e) H. Byrd, E. P. Suponeva, A. B. Bocarsly, M. E.
Thompson, Nature 1996, 380, 610.
excellent electrocatalytic performance with further optimizing
possibility by varying electrochemical conditions.
In conclusion, vertical step growth polymerization driven by
electrochemical stimuli with tunable interface function of
electrode was successfully developed via alternation of
reductive and oxidative reactions. Thanks to the controlled
electrochemical couplings and template effect of SAM, this
polymerization has not only fabricated vertical molecular wire on
electrode, also showed the sequence and topology controllable
possibility. The resulting surface confined molecular wire
presented fast electron transfer as well as SAM, and superior
electrocatalytic performance to general SAM and random
electropolymerized film widely used before. With rapid and
programmable electrochemical features, in principle for practical
applications, various types of metal complexes could be
introduced into molecular wire with sequence controllability in
one-pot or in alternative solutions. It is highly anticipated that this
simple polymerization can be generalized for practical molecular
interface relative applications with expectably superior
performances.
[9]
a) G. M. Credo, A. K. Boal, K. Das, T. H. Galow, V. M. Rotello, D. L.
Feldheim, C. B. Gorman, J. Am. Chem. Soc. 2002, 124, 9036; b) K.
Terada, H. Nakamura, K. Kanaizuka, M. Haga, Y. Asai, T. Ishida, ACS
Nano 2012, 6, 1988; c) G. Zeng, J. Gao, S. Chen, H. Chen, Z. Wang, X.
Zhang, Langmuir 2007, 23, 11631; d) M. D. Yilmaz, J. Huskens, Soft
Matter 2012, 8, 11768.
[10] a) A. B. Descalzo, R. Martínez-Máñez, F. Sancenón, K. Hoffmann, K.
Rurack, Angew. Chem. Int. Ed. 2006, 45, 5924; Angew. Chem. 2006,
118, 6068; b) F. Tancini, D. Genovese, M. Montalti, L. Cristofolini, L.
Nasi, L. Prodi, E. Dalcanale, J. Am. Chem. Soc. 2010, 132, 4781; c) T.
Ogoshi, S. Takashima, T. Yamagishi, J. Am. Chem. Soc. 2015, 137,
10962.
[11] a) C. Friebe, M. D. Hager, A. Winter, U. S. Schubert, Adv. Mater. 2012,
24, 332; b) B. J. Holliday, T. M. Swager, Chem. Commun. 2005, 23; c)
J. Heinze, B. A. Frontana-Uribe, S. Ludwigs, Chem. Rev. 2010, 110,
4724.
[12] P. M. Beaujuge, J. R. Reynolds, Chem. Rev. 2010, 110, 268.
[13] N. Haddour, J. Chauvin, C. Chantal Gondran, S. Cosnier, J. Am. Chem.
Soc. 2006, 128, 9693.
[14] a) D. L. Ashford, A. M. Lapides, A. K. Vannucci, K. Hanson, D. A.
Torelli, D. P. Harrison, J. L. Templeton, T. J. Meyer, J. Am. Chem. Soc.
2014, 136, 6578; b) F. Li, K. Fan, L. Wang, Q. Daniel, L. Duan, L. Sun,
ACS Catal. 2015, 5, 3786; c) L. Wang, K. Fan, Q. Daniel, L. Duan, F. Li,
B. Philippe, H. Rensmo, H. Chen, J. Sun, L. Sun, Chem. Commun.
2015, 51, 7883; d) D. L. Ashford, B. D. Sherman, R. A. Binstead, J. L.
Templeton, T. J. Meyer, Angew. Chem. Int. Ed. 2015, 54, 4778; Angew.
Chem. 2015, 127, 4860.
Acknowledgements
We are grateful to Prof. Zhaohui Su, Prof. Shengxiang Ji, and Dr.
Bo Liu in CIAC, and Prof. Katsuhiko Ariga, Dr. Jonathan P. Hill,
and Dr. Shinsuke Ishihara in NIMS, Japan for useful discussions.
This work was supported by the National Natural Science
Foundation of China (51573181, 21774121), the Hundred
Talents Program, CAS, China.
[15] a) L. Duan, L. Wang, F. Li, L. Sun, Acc. Chem. Res. 2015, 48, 2084; b)
V. Kunz, D. Schmidt, M. I. S. Röhr, R. Mitrić, F. Würthner, Adv. Energy
Mater. 2017, 7, 1602939; c) T. J. Meyer, M. V. Sheridan, B. D.
Sherman, Chem. Soc. Rev. 2017, 46, 6148; d) L. Duan, F. Bozoglian, S.
Mandal, B. Stewart, T. Privalov, A. Llobet, L. Sun, Nat. Chem. 2012, 4,
418; e) D. Wang, S. L. Marquard, L. Troian-Gautier, M. V. Sheridan, B.
D. Sherman, Y. Wang, M. S. Eberhart, B. H. Farnum, C. J. Dares, T. J.
Meyer, J. Am. Chem. Soc. 2018, 140, 719.
Keywords: step polymerization • single molecular assembly •
self-assembled monolayer • C-C coupling • electrochemistry
[16] Z. Fang, S. Keinan, L. Alibabaei, H. Luo, A. Ito, T. J. Meyer, Angew.
Chem. Int. Ed. 2014, 53, 4872; Angew. Chem. 2014, 126, 4972.
[17] M. Li, S. Ishihara, M. Akada, M. Liao, L. Sang, J. P. Hill, V. Krishnan, Y.
Ma, K. Ariga, J. Am. Chem. Soc. 2011, 133, 7348.
[1]
a) Z. Liu, A. A. Yasseri, J. S. Lindsey, D. F. Bocian, Science 2003, 302,
1543; b) T. Gupta, M. E. van der Boom, Angew. Chem. Int. Ed. 2008,
47, 5322; Angew. Chem. 2008, 120, 5402; c) A. Vilan, D. Cahen, Chem.
Rev. 2017, 117, 4624; d) A. Vilan, D. Aswal, D. Cahen, Chem. Rev.
2017, 117, 4248.
[18] a) M. Li, S. Kang, J. Du, J. Zhang, J. Wang, K. Ariga, Angew. Chem. Int.
Ed. 2018, 57, 4936; Angew. Chem. 2018, 130, 5030; b) M. Li, Chem.
Eur. J. 10.1002/chem.201803246.
[2]
[3]
a) V. Singh, P. C. Mondal, A. K. Singh, M. Zharnikov, Coord. Chem.
Rev. 2017, 330, 144; b) E. R. Dionne, A. Badia, ACS Appl. Mater.
Interfaces 2017, 9, 5607.
[19] a) C. Xia, R. C. Advincula, Chem. Mater. 2001, 13, 1682; b) Y. Lv, L.
Yao, C. Gu, Y. Xu, D. Liu, D. Lu, Y. Ma, Adv. Funct. Mater. 2011, 21,
2896; c) M. Oçafrain, T. K. Tran, P. Blanchard, S. Lenfant, S. Godey, D.
Vuillaume, J. Roncali, Adv. Funct. Mater. 2008, 18, 2163.
a) M. K. Brennaman, R. J. Dillon, L. Alibabaei, M. K. Gish, C. J. Dares,
D. L. Ashford, R. L. House, G. J. Meyer, J. M. Papanikolas, T. J. Meyer,
J. Am. Chem. Soc. 2016, 138, 13085; b) J. C. Wang, S. P. Hill, T.
Dilbeck, O. O. Ogunsolu, T. Banerjee, K. Hanson, Chem. Soc. Rev.
2018, 47, 104.
[20] a) B. Zhang, F. Li, R. Zhang, C. Ma, L. Chen, L. Sun, Chem. Commun.
2016, 52, 8619; b) Y. Tsubonouchi, S. Lin, A. R. Parent, G. W. Brudvig,
K. Sakai, Chem. Commun. 2016, 52, 8018; c) M. Schulze, V. Kunz, P.
D. Frischmann, F. Würthner, Nat. Chem. 2016, 8, 577.
[4]
a) P. Pallavicini, G. Dacarroa, Y. A. Diaz-Fernandezb, A. Taglietti,
Coord. Chem. Rev. 2014, 275, 37; b) A. Prꢀvoteau, K. Rabaey, ACS
Sens. 2017, 2, 1072.
[21] a) C. C. L. McCrory, S. Jung, J. C. Peters, T. F. Jaramillo, J. Am. Chem.
Soc. 2013, 135, 16977; b) Y. Yoon, B. Yan, Y. Surendranath, J. Am.
Chem. Soc. 2018, 140, 2397.
[5]
[6]
J. E. Greene, Appl. Phys. Rev. 2015, 2, 011101.
a) J. F. Stoddart, Acc. Chem. Res. 2001, 34, 410; b) N. Pavliček, L.
Gross, Nat. Rev. Chem. 2017, doi:10.1038/s41570-016-0005; c) R.
Otero, J. M. Gallego, A. L. Vázquez de Parga, N. Martín, R. Miranda,
Adv. Mater. 2011, 23, 5148.
[22] a) D. Bu, Y. Xiong, Y. N. Tan, M. Meng, P. J. Low, D.-B. Kuang, C. Y.
Liu, Chem. Sci. 2018, 9, 3438; b) Y. Zheng, A. J. Giordano, R. C.
Shallcross, S. R. Fleming, S. Barlow, N. R. Armstrong, S. R. Marder, S.
S. Saavedra, J. Phys. Chem. C 2016, 120, 20040; c) R. Sakamoto, S.
Katagiri, H. Maeda, H. Nishihara, Coord. Chem. Rev. 2013, 257, 1493;
d) R. Sakamoto, S. Katagiri, H. Maeda, Y. Nishimori, S. Miyashita, H.
Nishihara, J. Am. Chem. Soc. 2015, 137, 734.
[7]
[8]
a) R. B. Merrifield, Science 1965, 150, 178. b) R. B. Merrifield, Angew.
Chem. Int. Ed. 1985, 24, 799; Angew. Chem. 1985, 97, 801.
a) G. de Ruiter, M. Lahav, M. E. van der Boom, Acc. Chem. Res. 2014,
47, 3407; b) P. C. Mondal, V. Singh, M. Zharnikov, Acc. Chem. Res.
2017, 50, 2128; c) R. Sakamoto, K.-H. Wu, R. Matsuoka, H. Maeda, H.
[23] a) D. Lebedev, Y. Pineda-Galvan, Y. Tokimaru, A. Fedorov, N. Kaeffer,
C. Copꢀret, Y. Pushkar, J. Am. Chem. Soc. 2018, 140, 451; b) D. W.
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Shaffer, Y. Xie, D. J. Szalda, J. J. Concepcion, J. Am. Chem. Soc. 2017,
139, 15347.
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Entry for the Table of Contents (Please choose one layout)
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Vertical step-growth polymerization
of monomer A-B via individual A-A or
Jian Zhang, Jia Du, Jinxin Wang,
Yanfang Wang, Chang Wei, Mao Li*
B-B
coupling
driven
by
electrochemically
positive
and
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negative bias on self-assembled A or
electrode was developed for
synthesis of surface confined
molecular wire in single molecule
precision with sequence and
topology controlled possibilities.
B
Vertical Step-Growth Polymerization
Driven by Electrochemical Stimuli
from Electrode
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