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8Cite this: DOI: 10.1039/x0xx00000x

Vice-Versa Donor Acceptor Fluorene-Ferrocene

Alternate Copolymer: A Twisted Ribbon for
Electrical Switching
Chanchal Chakraborty, Manas Kumar Bera, Utpal Rana and Sudip Malik *

Received 00th January 2012,

Accepted 00th January 2012
DOI: 10.1039/x0xx00000x
www.rsc.org/

Two donor-acceptor type copolymers (PFFC-1 and PFFC-2)

containing

ferrocene

and

fluorene

moieties

have

been

successfully synthesized to evaluate redox triggered optical

and electronic properties. Interestingly, PFFC-1 shows twisted
ribbon like morphology at the liquid interface and turns into
micellar structure by switching oxidation .

Alternate conjugated co-polymers containing ferrocene

(Fc) units have attracted a great extent of attention due to
the optoelectronic properties of conjugated polymer and
the redox activity of the Fc units.1-2 As Fc is very electron
rich arene, it is easily oxidized to form ferrocenium cation
+
(Fc ) electrochemically or by weak oxidants. The most
successful way to incorporate Fc moieties in polymer
1,3-6
backbone involves covalent binding.
The major
aspiration to insert of the Fc moieties in a conjugated
polymer backbone is the evaluation of new materials to
7
8
be exploited as push-pull systems, molecular switches,
9
logic gates, and systems based on intramolecular charge
transfer.10 In this context, the choice of suitable bridging
ligands among metal centres is of prime importance.
Poly(fluorene)s (PFs) based copolymers are one of the
most potential blue light emitting materials for electronic
and optoelectronic application because of high quantum
yield and thermal stability.11 Selective substitutions by
electron donating dialkyl or electron withdrawing dicyano
derivative in 9-position of fluorene (Fl) can make these
either electronically rich fluorenes or electronically poor
fluorenes, respectively.
In this consequence, two new conjugated polymers
(Scheme 1) where functionalized Fl moieties would serve
the role of donor (PFFC-1) and acceptor (PFFC-2) viceversa have been designed to study the oxidation
behaviour of Fc of two polymers by common oxidizing
12
agents as well as the switching behaviour of donor-

This journal is The Royal Society of Chemistry 2012

acceptor conjugated polymers that are scarcely seen in

the literature 13, 14. In this aspect, we have synthesized
fluorene-ferrocene based two donor-acceptor copolymers
to explore by their photophysical, morphological, cyclic
voltammetry and electrical behaviours supported by
theoretical studies.

Scheme 1 Synthesis scheme for preparation of polymer PFFC-1 and PFFC-2.

Reagent and condition used: (I) CuBr2 on alumina, CCl 4, refluxed, 5 h (II) 1o
bromooctane, TBAB, KOH, H2 O, 75 C, 15 mins. (III) Acetic acid, CrO3, 6 h (IV) 1,1o
ferrocenediboronicacid, Pd(PPh3 )4, K2 CO3, argon, 85 C, 72 h. (V) Malononitrile,
o
o
110 C, 5 h (VI) 1,1-ferrocenediboronicacid, Pd(PPh3)4, K2 CO3, 85 C, 72 h.

Starting from the Fl, fluorene-ferrocene alternate copolymers were synthesized by proper selection of
monomer via Pd-catalyzed cross coupling polymerization
according to the Scheme 1. All the reaction steps and
characterization details are discussed in experiment
segment of electronic supplementary information (ESI).
All these steps provided satisfactory yields and polymers
produced a sufficiently high molecular weight (Mw) in GPC
study. PFFC-1 exhibited Mw = 11643 and PDI = 1.49,
whereas PFFC-2 unveiled Mw = 15,706 and PDI = 2.47 in
GPC using THF as eluent. In PFFC-1, we intentionally put
two dioctyl chains in 9-position of each Fl unit so that Fl
segment in PFFC-1 turns out to be electron rich unit. In
PFFC-2, a dicyano unit at 9-position of each Fl unit is put
to enrich the electron withdrawing capacity of Fl unit and

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Absorbance (a.u.)

1.0

Absorbance (a. u.)

PFFC-1
PFFC-2

1.2
0.8
0.6
0.4
0.2
0.0

400

600
Wavelength (nm)

800

PFFC-1
PFFC-2

0.02

0.01

0.00
600

650
700
Wavelength (nm)

2 | J. Name., 2012, 00, 1-3

750

Intensity (a.u.)

0.03

1.4

(a. u.)
Absorbance (a.u.)

Fe(ClO4)3 is different. Effect of addition of FeCl3 to PFFC1 and PFFC-2 are shown in Fig. 1c. After addition of
FeCl3 (50 M), a distinct colour change from yellow to red
is observed in PFFC-1 and it is possibly due to the
oxidation of electronically rich Fc centre to ferrocenium
+
cation (Fc ). Whereas, in PFFC-2, the yellow colour of the
polymer solution does not alter. Owing to the charge
transfer from Fc to cyanofluorene unit, Fc unit in PFFC-2
is electronically poor and oxidation is not feasible.
Addition of Fe(ClO4)3 to the solution of both polymers also
exhibit the similar results as FeCl3.
1
Oxidation of Fc unit in PFFC-1 is also confirmed by H
NMR titration upon successive addition of FeCl 3 to PFFC1 solution (ESI, Fig. S2). Titration studies suggest that
Fc is converted to Fc+ in PFFC-1 upon oxidation and the
protons of Fc unit are shifted to downfield (4.18 to 4.25
ppm and 4.45 to 4.58 ppm) than the same of pristine
PFFC-1. Subsequently, the d-d transition band (462 nm)
0.03
1.4
in UV-Vis spectra of PFFC-1 gets some red shifting to
2.5
5 (b)
PFFC-1
PFFC-1
1.2
(a) (b)
PFFC-1
PFFC-1
(a)
488 nm (Fig. 1b).
This
red shifting is owing to better
PFFC-1+FeCl
PFFC-2
3
PFFC-2
2.0
4
1.0
PFFC-1+FeCl
PFFC-2
0.02
electron
communication
after
oxidation of Fc centre to Fc+
PFFC-2+FeCl3
(b)
0.8 (a)
1.5
3
15
in PFFC-1. One broad charge transfer (CT) band
0.6
1.0
2
0.01
0.4
appears at NIR region at 980 nm (Fig. 1b) after oxidation
1
0.5
0.2
due to the LMCT transitions from Fl segment to Fc+ which
0
0.0
0.0
0.00
become
possible
due600to the generation of hole in the
600 400 650600
700
800
1000 750
350
400
450
500
550
400
600
800
Wavelength(nm)
(nm)
16
Wavelength
Wavelength
(nm)
Wavelength (nm)
metal-based
HOMO.
It is also visually confirmed by the
(a) (b)
colour change of the solution from yellow to red. Upon
(c)
(d) (e)
(f)
oxidation the photoluminescence intensity is enhanced 5
FeCl3
fold in case of PFFC-1 but not in PFFC-2 (Fig. 1c and
ESI, Fig. S3) owing to the better electronic
communication after oxidation to form Fc+.
Fig. 5.3: Optical color change on oxidation of CHCl3 solution of two copolymers by FeCl3.In cyclic voltammetry (CV) study referenced to the Fc/Fc+
Fig. 1(a)
of (d)
PFFC-1
and PFFC-2,
The enlarged portion betweenimage
(a) UV-vis
PFFC-2, spectra
(b) PFFC-1,
PFFC-2+FeCl
3 and (e) PFFC-1+FeCl3. (c) and (d) are
couple (ESI, Fig. S4), a reversible oxidation at E1/2 ox 0.05
wavelengths
range 600-750
nm
is givenbefore
in inset,
(b) oxidation
UV-vis spectra
of PFFC-1
of PFFC-1under
365 nm UV
irradiation
and after
respectively.
before and after oxidation by FeCl3 in CHCl 3. (c) Optical colour change on
V is assigned to the oxidation of Fc moiety of PFFC-1. A
oxidation of CHCl3 solution of two copolymers by FeCl 3. (I) PFFC-2, (II) PFFC-1, (IV)
small but significant peak at 0.9 V is attributed to
PFFC-2+FeCl 3 and (V) PFFC-1+FeCl 3. (III) and (VI) are images of PFFC-1 under 365
oxidation of Fl moiety of the copolymer. In PFFC-2, a very
nm UV irradiation before and after oxidation, respectively.
low peak due the reversible oxidation of Fc appears at
ox
Incorporation of Fc unit into PFFC alternate copolymer E1/2 0.002 V (ESI, Fig. S4) which indicate the oxidation
will influence the usual spectral properties of both Fl and is not facile. The polyfluorene oxidation peak appears at
Fc unit. In CHCl 3, PFFC-1 (Fig. 1a) shows two major 0.34 V. These values get some anodic shift because of
*
absorption bands, 328 nm ascribed to the - transition the incorporation of electron withdrawing cyanofluorene
in Fl segment and 462 nm for d-d transition of Fc moiety unit in PFFC-2 polymer. In PFFC-2, one strong reduction
red
*
with a small hump at ~300 nm that is - transition of Fc at E1/2 -1.52 V is ascribed to the cyanofluorene anion
moiety. PFFC-2 also reveals two characteristic formed owing to intramolecular charge transfer from
17
absorbance bands at ~ 360 nm and 495 nm in CHCl3 donor Fc to accepter cyanofluorene unit. The scan rate
solution. Absorption band for -* transition in Fc unit is dependent cyclic voltammetry studies (ESI, Fig. S5a-b)
also prominent in PFFC-2 ~ 300 nm. Unlike PFFC-1, a and linearity of the plot (ESI, Fig.S6a-b) of oxidative
small but well-defined charge transfer band is appeared peak current vs square root of the scan rate reveal the
at 663 nm in PFFC-2 (inset of Fig. 1a) that significantly oxidation is diffusion controlled in nature. Diffusion
-9
supports transfer of charge from donor Fc moiety to constants (D) derived by Cottrell equation are 3.310
-9
2
electron withdrawing cyanofluorene acceptor moiety. No and 8.710 cm /s for PFFC-1 and PFFC-2, respectively
such charge transfer band is observed in PFFC-1 as both which are consistent to the previously reported data of
this type main chain ferrocene copolymer.6
Fl and Fc are electron rich moieties.
It is important to note that oxidizing behaviour of both DFT optimized structures of PFFC-1, oxidized form of
polymers by common mild oxidizing agent like FeCl3 and PFFC-1 and PFFC-2 are given (Fig. S7a-c).
Corresponding images of HOMO and LUMO of each

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Fc acts as donor to produce an efficient charge transfer to

cyanofluorene segment. Both of the polymers are soluble
in common organic solvents like CH2Cl 2, chloroform, THF
etc. in room temperature. 1H NMR signals (ESI, Fig.S1)
of Fc and aromatic region of copolymer PFFC-1 and
1
PFFC-2 are compared. In both of the polymers, H
signals of Fc rings are seen as broad peaks in the range
of 4-5 ppm. In PFFC-2, Fc rings are associated with
electron withdrawing cyanofluorene units and as a result
1
of this H signals of Fc ring get a downfield shift to exhibit
1
higher value (5.01 and 4. 91 ppm) than Fc H signals of
PFFC-1 (4.44 and 4.13 ppm). Aromatic protons of
fluorene segments produce broad signals in the range of
7-8 ppm in both of the copolymers. Incorporation of
cyanofluorene unit in PFFC-2 is further evidenced by the
presence of stretching vibration (CN) at 2205 cm-1 in
FTIR spectra of PFFC-2.

Absorbance (a.u.)

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repeating units of copolymers (Fig. S8a-f) provide that the

HOMO and LUMO of PFFC-1 reside on and * orbital,
facilitating the -* transition. After oxidation of PFFC-1
by FeCl3, HOMO of the oxidized product resides on Fl
moiety and LUMO is on Fc+ (Fig. S8c-d), revealing a
possibility of charge transfer that is supported by the
presence of NIR band in UV-vis spectra (Fig.1b). In case
of PFFC-2, (Fig. S8e-f) the HOMO resides on Fc moiety
and LUMO is on Fl moiety. A charge transfer from Fc
(HOMO) to Fl (LUMO) in reverse direction is expected
and produces a CT band in UV-vis spectra at 663 nm in
inset of Fig. 1a.
Self
Assembly

(a)

Right Handed
Left Handed
Self
Assembly

55 m
m

(d)
(d)
(c)

(b)

Left handed

(e)
(e)
(d)

1 m1 m
5 m

Right handed
10 m
5 m

(e)

5 m

1 m

(f)(f)

5 m
5 m

(g)
(g)

5 m

2 2m
m

Fig.
(g)2 (a) Schematic representation of PFFC-1 self-assembly in methanol-hexane
interface to form twisted ribbon and micelles after oxidation. (b)-(e) PFFC-1 in
methanol-hexane interface and (d),(e) PFFC-1 in methanol-hexane interface after
oxidation by FeCl3. The red circled area in (b) indicating the right handed twisted
ribbon and the rests are left handed.
2 m

To investigate the morphological features of the PFFC-1

during oxidation, SEM studies have been performed by
making the interface layer of methanol and hexane (1:1)
mixture. Long twisted ribbon morphology of PFFC-1 chain
with ~1 m width is observed (Fig. 2b-e). From the SEM
image in Fig. 2b-c, it is evident that both left and right
handed twisted ribbons are present in our system. As
PFFC-1 contains Fc and Fl having two long alkyl chains,
some change in configuration of the polymer may occur
at the interface of polar and non-polar solvent.14a Fc part
may prefer the polar solvent and alkyl chains non-polar
solvent. This process may introduce some twisting of
dihedral angle in flexible Fc moieties to create some
twisting in individual polymer chains. The twisting of Fc
dihedral angle is recently investigated in ferrocene
naphthalenediimide donor-acceptor conjugate with long
18
alkyl chain. In the present system, the interface of polarnonpolar solvent plays the key role to twist the ferrocene
dihedral angle and subsequently it leads to the formation

This journal is The Royal Society of Chemistry 2012

of the left or right handed twisted polymer chains that are

successively self-assembled to manifest as the twisted
ribbon. The - stacking of fluorene unit and van der
Walls interaction between alkyl chains are responsible to
the self-assembly of individual twisted polymer chain.
This observed twisted ribbon morphology is similar to the
twisting of block co-polymers without having chiral group
and their controlled self-assemblies of helical structures
19
by mixed solvent effect. We have proposed a possible
schematic representation (Fig. 2a) based on this
phenomenon. Again, SEM studies of PFFC-1 polymer in
complete hexane or methanol solution do not produce
any characteristic morphology (ESI, Fig. S9). So, the
polar-nonpolar mixed solvent plays a crucial role to twist
the dihedral angle in Fc moieties and consequent selfassembly of individual twisted polymer chains.
To get insight about twisting, the circular dichroism (CD)
spectra were performed (ESI, Fig. S10). In CD spectra
of PFFC-1 in methanol and hexane (1:1), an induced CD
signals appeared at absorption peak of PFFC-1 supports
the presence
1 mof twisted aggregates in the solution. The
temperature dependent CD studies of PFFC-1 (ESI, Fig.
S11a) reveal the CD intensity (+ cotton effect) of Fc
twisting and the CD pattern are not influenced by
temperature. It suggests the presence of a stable twisting
in our system and it also rules out the possibility of
racemization at higher temperature. CD intensity is not
significantly changed with the decrease of PFFC-1
concentration (ESI, Fig. S11b). SEM images at various
(ESI, Fig. S12) also reveals that PFFC-1
2 concentration
m
forms the twisted structure even if at very low
concentration. These observations indicate the cotton
effect in the system is not an interchain phenomena.
Chirality generated in PFFC-1 is form dihedral angle
twisting of Fc units which is not dependent on
concentration. Upon oxidation, PFFC-1 generates an
+

ionic Fc group that together with Cl counter ions will

assemble to form the inside of the micelle with the
hydrophobic alkyl chains facing outwards in the solution
in order to maximize ionic interactions (Fig. 2d-e).
Structural rearrangements of this type have been
reported earlier by Manners et al. for Fc containing block
copolymers.20 The CD spectra (ESI, Fig. S10) of PFFC-1
after oxidation also demonstrates no signal as polymer
chains get micellar aggregation.
Charge transfer complex between a metal centre and
organic chromophore provides a novel system for
memory application because formation of metal filament
through redox reaction as well as intermolecular charge
15,21
transfer.
To explore the electrical property of the
polymers, current density(J)voltage (V) characteristics of
the
ITO/PEDOT:PSS/PFFC-1/Al
and
ITO/PEDOT:PSS/PFFC-2/Al at room temperature are
compared in Fig. 3a-b. The device made of PFFC-1
shows an excellent conductance with switching behaviour
whereas the device made of PFFC-2 does not produce

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this type of switching performance. Initially, PFFC-1 is in

a low-conducting state (OFF-state). When the bias
voltage is increased to ~2 V, a transition from the OFFstate to a higher conducting state (ON-state) occurs with
a moderate ON/OFF ratio~40, presumably because of the
+ 15
oxidation of Fc groups to Fc . Formation of Fc+ in
PFFC-1 by electrical oxidation generates holes in the
16
metal-based HOMO and it enhances the conductivity.
+
During a sweep at 2 V, substantial number of Fc is
formed due to oxidation of Fc and makes continuous
conducting channel between the electrodes resulting in
+
an increment in current. At reverse voltage Fc is reduced
to Fc which blocks the conducting channel. 15 Ability of
chemical oxidation of PFFC-1 is previously confirmed
optically and electrochemically by addition of FeCl 3
solution whereas PFFC-2 is reluctant to oxidation which is
previously confirmed, so it does not produce any
conductance switching in increasing forward bias.

(a)

(b)

Polymer Science Unit, Indian Association for the Cultivation of Science,

2A & 2B Raja S. C. Mullick Road, Jadavpur, Kolkata 700032.
Electronic Supplementary Information (ESI) available: [Details of
synthesis and characterization by instrumental techniques, 1 H-NMR, PL,
CV,

DFT

calculations

and

SEM

images.].

See

Y. Morisaki and Y. Chujo, Macromolecules, 2003, 36, 9319; G.

539.

H. Khalid, H. Yu, L. Wang, W. A. Amer, M. Akram, N. M. Abbasi,

Z. ul-Abdin and M. Saleem, Polym. Chem., 2014,5, 6879.

S. R. Gonzlez, M. C. R. Delgado, R. Caballero, P. D. Cruz, F.

Langa, J. T. L. Navarrete and J. Casado, J. Am. Chem. Soc., 2012,
134, 5675.

L. Tan, M. D. Curtis and Y. Francis, Macromolecules, 2002, 35,

4628.

K. Naka, T. Uemura and Y.Chujo, Macromolecules, 2000, 33, 6965.

T. Yamamoto, T. Morikita, T. Maruyama, K. Kubota and M. Katada,

Macromolecules, 1997, 30, 5390; T. Morikita and T. Yamamoto, J.
Organomet. Chem., 2001, 637-639, 809.

Fig. 3 (a) The JV characteristics of ITO/PEDOT:PSS/PFFC-1/Al and

ITO/PEDOT:PSS/PFFC-2/Al devices at room temperature. (b) Schematic
representation of cross section of the device used for J-V characterization.

In summary, two donor-acceptor type copolymers, PFFC1 and PFFC-2, containing Fc and fluorene moieties have
been
successfully
designed
and
synthesized.
Intramolecular charge transfer from Fc to cyanofluorene
segments in PFFC-2 is confirmed by appearance of
charge transfer band in UV-vis spectra. Oxidation of Fc
centers to Fc+ either by chemically or electrically
generates holes in metal HOMO to produce better
electronic communication in copolymer that reflects in
enhancement of PL intensity and as well as the switching
behaviour between low-conducting state (OFF-state) to a
high conducting state (ON-state) in J-V measurements of
PFFC-1. Interestingly, the PFFC-1 shows twisted ribbon
morphology with an induced CD signal due to solvent
induced twisting in polymer chain and turns into micellar
structure by triggering oxidation. This study has
tremendous impact on the correlation among preparation
of donor-acceptor ferrocene based copolymers and its
oxidation triggered morphological aspects with electronic
properties.
Dr. Malik acknowledges CSIR, INDIA (project no.
02(0161)/ 13/EMR-II) for the partial support of finance. M.
K. Bera is thankful to CSIR, New Delhi, India for the
fellowship.

J. Zyss, I. Ledoux, S. Volkov, V. Chernyak, S. Mukamel, G. P.

Bartholomew and G. C. Bazan, J. Am. Chem. Soc., 2000, 122, 11956.

J. Jiao, G. J. Long, F. Grandjean, A. M. Beatty and T. P. Fehlner, J.

Am. Chem. Soc., 2003, 125, 7522.

4 | J. Name., 2012, 00, 1-3

studies,

Masson, A. J. Lough and I. Manners, Macromolecules, 2008, 41,

I-V
Al
Polymer
PEDOT:PSS
ITO
Glass

Notes and references

CD

DOI: 10.1039/c000000x/

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