Tetrablock Metallopolymer Electrochromes

Article abstract of DOI:10.1002/anie.201712945

Multi-block polymers are highly desirable for their addressable functions that are both unique and complementary among the blocks. With metal-containing polymers, the goal is even more challenging insofar as the metal properties may considerably extend the materials functions to sensing, catalysis, interaction with metal nanoparticles, and electro- or photochrome switching. Ring-opening metathesis polymerization (ROMP) has become available for the formation of living polymers using highly efficient initiators such as the 3rd generation Grubbs catalyst [RuCl₂(NHC)(=CHPh)(3-Br-C₅H₄N)₂], 1. Among the 24 possibilities to introduce 4 blocks of metallopolymers into a tetrablock metallocopolymer by ROMP using the catalyst 1, two viable pathways are disclosed. The synthesis, characterization, electrochemistry, electron-transfer chemistry, and remarkable electrochromic properties of these new nanomaterials are presented.

Full text of DOI:10.1002/anie.201712945

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Accepted Article
Title: Tetrablock Metallopolymer Electrochromes
Authors: Didier Astruc, Haibin Gu, Roberto Ciganda, Patricia Castel,
Sergio Moya, Ricardo Hernandez, and Jaime Ruiz
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Tetrablock Metallopolymer Electrochromes
Haibin Gu, Roberto Ciganda,* Patricia Castel, Sergio Moya, Ricardo Hernandez, Jaime Ruiz,
Didier Astruc*
th
This article is dedicated to Prof. Dr. Michel Pouchard (ICMCB, Bordeaux) at the occasion of his 80 birthday
Abstract: Multi-block polymers are highly desirable for their
addressable functions that are both unique and complementary
among the blocks. With metal-containing polymers, the goal is even
more challenging insofar as the metal properties may considerably
extend the materials functions to sensing, catalysis, interaction with
metal nanoparticles and electro- or photochrome switching. Ring-
opening-metathesis polymerization (ROMP) has become available
are ferrocene (FcH) and 1,2,3,4,5-pentamethylferrocene (Fc*H)
[
6]
that are oxidizable to 17-electron isostructual cations, and the
-
-
[11]
hexafluorophosphate salts (X = PF
6
) of cobalticinium (CcH)
)] ,(FbH), isolobal to ferrocene, reducible to
their neutral 19-electron counterparts without structural change
6
+
6 6
and [FeCp(η -C Me
[
12]
of the sandwich unit.
These metal sandwich complexes have previously been
for the formation of living polymers using highly efficient initiators
used to synthesize monomers 7-10 that are polymerizable to
rd
[9a,10]
such as the 3 generation Grubbs catalyst [RuCl
2
(NHC)(=CHPh)(3-
living metallopolymers by ROMP using the catalyst 1
Br-C
5
H
4
N)
2
], 1. Among the 24 possibilities to introduce 4 blocks of
(Scheme 1).
metallopolymers into a tetrablock metallocopolymer by ROMP using
the catalyst 1, we have disclosed two viable pathways. The
synthesis, characterization, electrochemistry, electron-transfer
chemistry and remarkable electrochromic properties of these new
nanomaterials are presented herein.
Interest in metallopolymers has recently emerged due to
their multiple properties as memory devices, conductive,
luminescent
and
photovoltaic
materials,
catalysts,
[
1]
electrocatalysts and artificial metalloenzymes. Metal fragments
[
2]
are rarely stable in multiple redox forms, however.
transition-metal compounds that disclose several redox states
involve color changes. These variations bring about
Yet
[
2]
[
3]
photochrome and electrochrome properties due to changes in
d à d transition that are responsible for absorption in the visible
[
4]
spectrum range. This concept has been pioneered with the
ferrocene-ferricinium group in readily polymerizable systems by
[
1b,5]
Manner’s group.
Indeed, not only polyferrocene materials are
but also diblock metallopolymers including a
ferrocene block and another organometallic block have been
[
5,6]
numerous,
rd
Scheme 1. The 3 -generation Grubbs catalyst 1, four redox-robust sandwich
units and their corresponding monomers 7-10 used for ROMP reactions.
[
7]
recently reported with a variety of materials properties. In
particular, the use of very efficient ring-opening-metathesis
rd
polymerization (ROMP) catalysts such as the 3 -generation
The neutral monomers 7 and 8 were polymerized in
dichloromethane (DCM), and the cationic monomers 9 and 10 in
dimethylformamide (DMF). The polymerization rates must be
taken into account (as the polymer solubility) for the synthesis of
[
8]
Grubbs catalyst [RuCl
2 5 4 2
(NHC)(=CHPh)(3-Br-C H N) ], 1, (NHC
=
1,3-dimesityl-imidazolyl-2-ylidene) has allowed the synthesis
[
7b,9]
of living ferrocene-containing and di-block metallopolymers.
We now wish to benefit from the excellent catalytic
properties of 1 providing living polymers to combine electron-
reservoir late transition-metal sandwich systems spanning a
broad redox scale in the construction of multi-block
electrochrome metallocopolymers containing up to four blocks.
The four redox-robust sandwich units (see Scheme 1) involved
the multi-block metallocopolymers, and the rate order is 8 > 7 >
[13]
9
> 10. The later polymerization is marred by the combination
of positive charge and arene ligand bulk. Thus, among the 24
theoretical possibilities to assemble the four blocks, in practice
only two routes are found feasible and are shown in Scheme 2.
In all cases the monomer/ catalyst 1 feed ratio for each block is
2
2
5, and kinetics analyses are conducted at room temperature (rt,
1
2 ± 1°C) until the polymerization is quantitative as shown by H
[
a]
b]
Dr H. Gu, Key Laboratory of Leather Chemistry and Engineering of
Ministry of Education, Sichuan University, Chengdu 610065, China
Drs R. Ciganda, P. Castel, J. Ruiz, Prof. D. Astruc, ISM, UMR
CNRS 5255, Univ. Bordeaux, 33405 Talence Cedex, France.
E-mail: r.ciganda@hotmail.com; didier.astruc@u-bordeaux.fr
Dr Ciganda, R. Martinez, Facultad de Chimica de San Sebastian,
Universidad del Pais Vasco, Apdo 1072, 20080 San Sebastian,
Spain.
NMR analysis (see the Supplementary Information, SI, for
1
[
complete procedure, reaction times and H NMR analysis). For
both routes, the first block introduced is that of 8, because it
provides the fastest polymerization due to its better solubility,
and it renders the subsequent copolymers more soluble than
when they are alone. In the first route the introduction order
involves first the two neutral blocks 8, then 7, followed by 10, all
[c]
Supporting information for this article is given via a link at the end of
the document.
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COMMUNICATION
2 2 2 2 2 2
Scheme 2. Synthesis of the two tetrablock metallocopolymers 14 and 17. I: 1 in CH Cl , r. t. 10 min; II: 7 in CH Cl , r. t. 15 min; III: 9 in CH Cl , r. t. 10 min; IV: 10
in DMF r. t. overnight; V: 9 in CH Cl , r. t. 10 min; VI: 7 in CH Cl , r. t. 20 min; VII: 10 in DMF r. t. overnight.
2 2 2 2
three in DCM, leading to the triblock co-polymer 13. The fourth
block 9 is introduced in DMF to the DCM solution of the Ru-
ended triblock copolymer 13. Thus the overall order of
introduction is 8-7-10-9 leading to the tetrablock copolymer 14
according to the sequence 8à11à12à13à14. In the second
route, the introduction of the neutral and cationic groups is
alternated in DCM, this introduction order 8-10-7-9, all in DCM at
rt, leading to the tetrablock copolymer 17 according to the
sequence 8 à11à15à16à17 (Scheme 2 and Table 1).
gated by cyclic voltammetry (CV) using decamethylferrocene,
[
14]
[FeCp*
2
],
4 6
as the internal reference and [n-Bu N][PF ] as the
supporting electrolyte and compared with those of the
corresponding homopolymers and diblock copolymers (Figure
1). DCM was used as the solvent for diblock copolymer 12 and
the homopolymers of 7 and 8, whereas DMF was used as the
solvent for the homopolymers of 9 and 10 and copolymers 13,
14, 15, 16 and 17. The E1/2, ∆E and i
c a
/i data measured vs.
[FeCp* ] are gathered in Tables S3, S7, S10, S13, S16 and S20
2
The electrochemical properties of the copolymers were investi-
of SI. All of the waves are chemically and electrochemically
reversible with slight broadening for the cathodic waves of the
[
15]
Cc and Fb groups due to electrostatic effects. This broadening
means that all of the cationic redox centers of the same nature
are not completely equivalent in these polymers due to steric
constraints inside the polymer framework. Interestingly, the CV
of the Fb units is considerably more flattened in the tetrablock
copolymer 17 than in 14, which is best taken into account by the
fact that the cationic Fb centers are more buried inside the
copolymer in 17 than in 14. Since Fb is the bulkiest unit due to
Table 1. Polymerization degrees for each block in the tetrablock copolymers
1
4 and 17.
[
a]
[b]
[c]
[d]
Copolymer
Block
Fc*
Conv (%)
>99
n
p1
n
p2
n
p3
25
25
25
25
25
25 ± 1
25 ± 1
22 ± 3
25 ± 3
25 ± 1
30 ± 5
20 ± 5
28 ± 5
20 ± 5
27 ± 5
Fc
>99
1
4
the C
6 6
Me ligand, the electrostatic difference among the identical
FbX
Cc*
Fc*
>99
[
16]
Fb redox centers is more marked in 17 than in 14.
[
17]
>99
The Bard-Anson electrochemical method
usually is reliable
for the estimation of the number of monomer units in redox-
robust metallopolymers of relatively modest size such as those
>99
[
17]
p
involved here. In the CV measurement, the total number (n )
FbX
Fc
>99
>99
>99
25
25
25
22 ± 3
25 ± 2
26 ± 3
7
of electrons transferred in the redox wave of each redox center
in the copolymer 13 should be the same as that of the
corresponding monomer units in the copolymer, as only one
electron is transferred from the cathode or to the anode for each
1
7
22 ± 5
15
Cc*
redox center. This electron number
p
n for each block is
1
[
a] Monomer conversion determined by H NMR. [b] Polymerization degree
[17]
1
calculated using Bard−Anson’s empirical equation 1.
obtained by H NMR using monomer conversion. [c] Polymerization degree
1
determined by H NMR end-group analysis. [d] Degree of polymerization
[
17]
calculated using the Bard-Anson method. The values for Fb and Cc much
lower than the feed ratio (25) are due to wave broadening resulting from lack
of equivalence of the redox centers of same nature (see text).
(idp /C ) M
(equation 1)
p
p
0.275
np =
(
)
(
idm /C ) M
m
m
d
The i , M, and C are the CV wave intensity of the diffusion
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COMMUNICATION
current, molecular weight, and concentration of the monomer
Based on the redox potentials observed by CV (Figure 1),
[
6,11b]
(
m) and polymer (p), respectively (see n
p
in Tables S8 and S18
suitable redox reagents with known redox potentials
(Figure
of SI). The numbers of electrons found are between 20 and 30
for theoretical numbers of 25, except in the case of the Fb units
for which the values are lower due to the electrostatic-based
wave broadening (vide supra and Table 1).
2) are added stoichiometrically vs. a given block to the tetrablock
copolymer 14 in order to provide exergonic electron-transfer
reactions. A difference of 0.12 V between the redox potentials of
the reagent and the given redox centers of the copolymer
provides
a 99% yield at 22°C for such reversible redox
The determination of these numbers of units in each block
[6a]
reactions. Selective color changes upon addition of the redox
reagents are shown in Figures 2 and 3.
1
are fine by HNMR, including end-group analysis. The
electrochemistry results are less precise (n = 25 ± 5). They
become erratic for the numbers of cationic redox centers in 17 in
which neutral and cationic blocks are alternating, in particular for
the bulky Fb centers presumably for steric packing reasons.
Figure 2. Electrochromic activity of the tetrablock copolymer 14: selective
color changes upon selective oxidation and reduction reactions of the
tetrablock copolymer 14 (framed in yellow on the right side) by stoichiometric
amounts of redox reagents with precise redox potentials insuring exergonic
redox reactions (see UV-vis. in SI). On the right side, the blocks are
6
represented by the metal, and FE for the [FeCp(η -C
6
Me
6
)]-based block.
Figure 1 Compared CVs of the homopolymers of 7 (a, in CH
CH Cl ), 9 (c, in DMF) and 10 (d, in DMF), triblock copolymers 13 (e, in DMF)
and 16 (f, in DMF), and tetrablock 14 (g, in DMF) and 17 (h, in DMF). Internal
2 2
Cl ), 8 (b, in
Figure 3. Electrochromic activity of the tetrablock copolymer 14: reaction of
HAuCl with 14 selectively oxidizes its 25 Fc* centers to green 14[Cl]25 and
2
2
4
*
reference: [FeCp
2
]; reference electrode (0.0V): Ag; working and counter
N][PF ].
ligand-stabilized AuCl that disproportionates overnight at rt, finally producing
very large globular purple Au nanoparticles with 130 ± 5 nm size (see SI).
electrodes: Pt; scan rate: 0.4 V/s; supporting electrolyte: 0.1 M [n-Bu
4
6
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COMMUNICATION
+
-
Figure 2 shows that addition of colorless NO PF
vs. FeCp* ) to 14 in DCM oxidizes the 25 Fc* centers (E1/2
.36V vs. FeCp* ) of 14 with an exergonic driving force of 1.18 V
yielding the olive-green polymer 14[PF 25. Oxidation of 14 with
HAuCl in THF (Figure 3) also gives an olive-green color that
slowly turns light-purple, however, the color of Au nanoparticles
6
(E° = 1.54 V
[5]
a) D. A. Foucher, B. Z. Tang, I. Manners, J. Am. Chem. Soc. 1992, 114,
6
246-6248; b) X. Wang, G. Guerin, H. Wang, Y. Wang, I. Manners,
2
=
Science 2007, 317, 644-647; c) A. D. Russell, R. A. Musgrave, L. K.
Stoll, P. Choi, H. Qiu, I. Manners, J. Organomet. Chem. 2015, 784, 24-
0
2
6
]
3
0.
4
[
[
6]
7]
a) D. Astruc, Electron-Transfer and Radical Processes in Transition
Metal Chemistry, VCH, New York, 1995; b) D. Astruc, Eur. J. Inorg.
Chem. 2017, 6-29.
(
AuNPs with 130-nm core, Figures S82 and S83) due to slow
[
10a,18]
a) L. Chabanne, I. Matas, S. K. Patra, I. Manners, Polym. Chem. 2011,
2, 2651-2660; b) J. B. Gilroy, S. K. Patra, J. M. Mitchels, M. A. Winnik, I.
Manners, Angew. Chem. Int. Ed. 2011, 50, 5851-5855; c) R H. Staff, M.
Gallei, M. Mazurowski, M. Rehahn, R. Berger, K. Landfester, D. Crespy,
ACS Nano 2012, 6, 9042-9049; d) N. McGrath, F. H. Schacher, H. Qiu,
S. Mann, M. A. Winnik, I. Manners, Polym. Chem. 2014, 5, 1923-1929;
e) A. S. Abd-El-Aziz, C. Agatemor, N. Etkin, Macromol. Rapid Commun.
2014, 35, 513-559; f) C. G. Hardy, J. Zhang, Y. Yan, L. Ren, C. Tang,
Prog. Polym. Sci. 2014, 39, 1742-1976; g) J.-F. Lutz, J.-M. Lehn, E. W.
Meijers, K. Matyjaszewski, Nat. Mater. Rev. 2016, 1, 16024; h) A. S.
Campbell, H. Murata, S. Carmali, K. Matyjaszewski, M. F. Islam, A. J.
Russel, Biosens. Bioelectron. 2016, 86, 446-453; i) K. Y. Zhang, S. J.
Liu, Q. Zhao, W. Huang, Coord. Chem. Rev. 2016, 319, 180-195; j) D.
Scheid, M. von der Luhe, M. Gallei, Macromol. Rapid Commun. 2016,
disproportionation of the Au(I) intermediate.
Addition in
25 oxidizes its
) with an exergonic driving
force of 0.92 V yielding the green polymer 14[PF 50 (Figure 2).
Selective reductions with color change proceed similarly in
DMF/THF. Addition of light brown 1,2,3,4,5-Me -CcH (E° = -1.10
V vs. FeCp* ) to 14 specifically reduces its 25 CcX centers (E° =
0.71 V vs. FeCp* ) with an exergonic driving force of 0.39 V
yielding the orange reduced polymer. Subsequent addition of
% Na/Hg (E° = - 1.61 V vs. FeCp* ) reduces the 25 Fb centers
E° = 0.56 V vs. FeCp* ) with an exergonic driving force of 0.12
+
-
DCM of additional NO PF
6 6
to olive-green 14[PF ]
2
5 Fc centers (E° = 0.62 V vs. FeCp*
2
6
]
5
2
-
2
1
2
(
2
V yielding a neutral deep-green form of polymer 14 (Figure 2).
3
7, 1573-1580; k) S. Schoettner, R. Hossain, C. Ruetiger, M. Gallei,
Polymers 2017, 9, 491.
[
[
[
8]
9]
a) J. A. Love, J. P. Morgan, T. M. Trnka, R. H. Grubbs, Angew. Chem.
Int. Ed. 2002, 41, 4035-4037; b) C. W. Bielawski, R. H. Grubbs, Prog.
Polym. Chem. 2007, 32, 1-29; G. C. Vougioukalakis, R. H. Grubbs,
Chem. Rev. 2010, 110, 1746-1787.
In conclusion, the first tetrablock metallocopolymers have been
synthesized with 25 metallo-units in each bock using the very
efficient Ru ROMP catalyst 1. The design of the robustness of
the four distinct redox-robust centers allows electrochemical
redox cascades and various color changes upon addition of
exergonic redox reagents of suitable redox potentials, which
forms rich multi-color electrochromes. A forthcoming challenge
will involve film technology.
a) H. Gu, A. Rapakousiou, P. Castel, N. Guidolin, N. Pinaud, J. Ruiz, D.
Astruc, Organometallics 2014, 33, 4323-4335; b) H. Gu, R. Ciganda, R.
Hernández, P. Castel, A. Vax, P. Zhao, J. Ruiz, D. Astruc, Polym.
Chem. 2016, 7, 2358-2371.
10] a) H. Gu, R. Ciganda, P. Castel, A. Vax, D. Gregurec, J. Irigoyen, S.
Moya, L. Salmon, P. Zhao, J. Ruiz, R. Hernández, D. Astruc, Chem.-
Eur. J. 2015, 21, 18177-18186; b) H. Gu, R. Ciganda, R. Hernandez, P.
Castel, P. Zhao, J. Ruiz, D. Astruc, Macromolecules 2015, 48, 6071-
6076.
Acknowledgements
[
[
[
11] a) J. E. Sheats, M. D. Rausch, J. Org. Chem. 1970, 35, 3245-3249; b)
For redox potentials of various ferrocene and cobaltocene complexes,
see N. G. Connelly, W. E. Geiger, Chem. Rev. 1996, 96, 877-910.
12] a) A. S. Abd-El-Aziz, S. Bernardin, Coord. Chem. Rev. 2000, 203, 219-
Financial support from Gobierno Vasco (R. C., post-doctoral
scholarship), the Universidad del Païs Vasco, the Universities of
Bordeaux and Sichuan, Chengdu, China, CIC biomaGUNE and
the CNRS is gratefully acknowledged
2
67; b) J.-R. Hamon, D. Astruc, P. Michaud, J. Am. Chem. Soc. 1981,
03, 758-766.
1
13] For reviews of ROMP reactions initiated by 1 with late transition-metal
metallocenes in the side chains, see a) I. Dragutan, V. Dragutan, B. C.
Simionescu, A. Demonceau, H. Fisher, Beilstein J. Org. Chem. 2015,
Keywords: electrochrome • copolymer • redox activity • electron
transfer • metallocene
1
1, 2747-2762; b) I. Dragutan, V. Dragutan, P. Filip, B. C. Simionescu,
A. Demonceau, Molecules 2016, 21, 198.
[
1]
a) A. S. Abd-El-Aziz, P. O. Shipman, B. N. Boden, W. S. McNeil, Prog.
Polym. Sci. 2010, 35, 714-836; b) G. R. Whittell, M. D. Hager, U. S.
Schubert, I. Manners, Nat. Mater. 2011, 10, 176-188; c) F. H. Schacher,
P. A. Rupar, I. Manners, Anew. Chem. Int. Ed. 2012, 51, 7898-7921; d)
A. S. Abd-El-Aziz, E. A. Strohm, Polymer 2012, 53, 4879-4921; e) J. W.
Zhou, G. R. Whittell, I. Manners, Macromolecules 2014, 47, 3529-3543;
f) C. Deraedt, A. Rapakousiou, Y. Wang, L. Salmon, M. Bousquet, D.
Astruc, Angew. Chem. Int. Ed. 2014, 53, 8445-8449; g) H. B. Qiu, Z. M.
Hudson, M. A. Winnick, I. Manners, Science 2015, 347, 1329-1332; h)
R. L. N. Hailes, A. M. Oliver, J. Gwyther, G. R. Whittell, I. Manners,
Chem. Soc. Rev. 2016, 45, 5358-5407; i) R. Schroot, M. Jäeger, U. S.
Schubert, Chem. Soc. Rev. 2017, 46, 2754-2798.
[
[
14] a) I. Noviandri, K. N. Brown, D. S. Fleming, P. T. Gulyas, P. A. Lay, A.
F. Masters, L. J. Philips, J. Phys. Chem. B 1999, 103, 6713-6722; b) J.
Ruiz, M.-C. Daniel, D. Astruc, Can. J. Chem. 2006, 84, 288-299.
15] A. J. Bard, L. R. Faulkner, Electrochemical Methods: Fundamentals
nd
and Applications, 2 ed., Wiley, New York, 2001.
[16] F. Barrière, W. E. Geiger, J. Am. Chem. Soc. 2006, 128, 3980-3989; b)
A. K. Diallo, J.-C. Daran, F. Varret, J. Ruiz, D. Astruc, Angew. Chem.
Int. Ed. 2009, 48, 3141-3145; c) W. E. Geiger, F. Barrière, Acc. Chem.
Res. 2010, 43, 1030-1039; d) A. K. Diallo, C. Absalon, J. Ruiz, D.
Astruc, J. Am. Chem. Soc. 2011, 133, 629-641.
[
[
2]
3]
F. A. Cotton, G. Wilkinson, C. A. Murillo, M. Bochmann, Advanced
th
[17] J. B. Flanagan, S. Margel, A. J. Bard, F. C. Anson, J. Am. Chem. Soc.
1978, 100, 4248-4253.
Inorganic Chemistry, 6 Ed., Wiley, New York, 1999.
nd
a) Photochromism: Molecules and Systems, 2 Ed. (Eds.: H. Dürr, H.
[
18] M.-C. Daniel, D. Astruc, Chem. Rev. 2004, 104, 293-346.
Bouas-Laurent) , Elsevier, Amsterdam, 1990; b) P. M. S. Monk, R. J.
Mortimer, D. R. Rosseinsky, Electrochromism and Electrochromic
Devices, Cambridge Editions, 2007.
[
4]
G. L. Geoffroy, M. S. Wrighton, Organometallic Photochemistry,
Academic Press, Cambridge, Mass., 2012.
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COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Two tetrablock metallocopolymers
composed of polymers of norbornene
derivatives with four distinct redox-
robust metallocenic redox centers in
the side chains were assembled by
ROMP; they showed extended redox
cascades and multi-electrochromic
behavior using adequate redox
reagents.
Haibin Gu, Roberto Ciganda,* Patricia
Castel, Sergio Moya, Ricardo Hernadez,
Jaim Ruiz, Didier Astruc*
Page No. – Page No.
Tetrablock Metallopolymer
Electrochromes
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