One-Pot Synthesis of Defect-Free Regioregular Poly(3-hexylthiophene) via Nickel Zero Catalyzed

Kumada Catalyst-Transfer Polymerization

Dattatray L. Tarange,† Sreelekha P.Gopinathan,‡ Anshu Kumar,† Naresh Chandrasekaran,†† Aditya Sad-
hanla,# Richard H. Friend,# Christopher R. McNeill,$ Dinesh Kabra,†††Anil Kumar*†‡§
†
Department of Chemistry, Indian Institute of Technology Bombay, India
‡
Centre for Research in Nanotechnology & Science, Indian Institute of Technology Bombay, India
§
Centre for Excellence in Nanoelectronics, Indian Institute of Technology Bombay India
††
IITB-Monash Research Academy, Indian Institute of Technology Bombay India
$ Department of Materials Science and Engineering, Monash University, Australia
# Cavendish Laboratory, University of Cambridge, UK
†††
Department of Physics, Indian Institute of Technology Bombay, India

Supporting Information
ABSTRACT:100% regioregular poly(3-hexylthiophene), (defect-free rr-P3HT), was synthesized in one-
pot via a soluble nickel zero catalyzed ex-situ Kumada catalyst-transfer polymerization. This is the first
example of a Ni(0) catalyzed Kumada catalyst-transfer polymerization. Ni(0) catalyst was synthesized
in quantitative yield using a conventional, off the shelf, Ni(II) catalyst. The catalyst was found to be
highly stable in solution at ambient conditions and hence can be prepared in advance and stored.
Polymerization follows a pseudo-living mechanism wherein the final molecular weight can be con-
trolled by monomer to initiator ratio. The process was found to be amenable for continuous flow process
resulting in the synthesis of rr-P3HT with very low polydispersity (1.1). We have also shown that the
current process has excellent batch-to-batch reproducibility even at large scale making it economically
viable for bulk production for large area applications. Furthermore, Urbach energy calculations as well
as solar cell device studies were carried out in order to explore the application of the 100% rr-P3HT for
various optoelectronic devices. A 15% improvement in photovoltaic efficiency was found using our de-
fect-free rr-P3HT as compared to conventional rr-P3HT.

INTRODUCTION the synthesis of rr-P3HT with defined chain end

One of the main driving forces for organic elec-
tronics is the possibility of large-scale printing of
optoelectronic devices at low cost and in a rela-
tively benign environment. In this direction, regi-
oregularpoly(3-hexylthiophene), rr-P3HT, is one
of the extensively synthesized and studied conju-
gated polymers for various optoelectronic device
applications.1-7 Grignard Metathesis (GRIM)
polymerization via Kumada Catalyst-Transfer
Polymerization (KCTP) is the most commonly
used methods for the synthesis of rr-P3HT.3,8-10
Mukundan and coworkers studied the kinetics of
GRIM polymerization and provided methods for
resulting in the synthesis of block copolymers.11
Elsa Reichmanis group has done pivotal work in
understanding the effect of processing conditions
on optoelectronic properties in case of rr-
P3HT.12-14 GRIM polymerization method, com-
monly referred to as in-situ initiation, via KCTP
involves the formation of a tail-to-tail (T-T) cou-
pled dimer that then initiates the polymerization
via the iterative sequence of oxidative addition,
transmetalation and reductive elimination result-
ing in the formation of rr-P3HT with minimum
one defect (T-T) per chain.5,15 Apart from the in-
ability to synthesize 100% rr-P3HT(defect-free
rr-P3HT), another major drawback of the in-situ
KCTP synthesis of rr-P3HT is poor batch-to-
batch reproducibility and broad polydispersity on
bulk synthesis. Interestingly these variations in
molecular properties significantly affect the final
device properties.16-19 Therefore, this hampers
the development of large area applications based
on rr-P3HT. We believe that the lack of repro-
ducibility is mainly due to the insolubility of the
catalyst in polymerization solvent coupled with
fast polymerization rate(polymerization is gener-
ally over within few minutes). Therefore, when
the batch size increases, the addition of large
amount of solid catalysts results in heterogeneous
initiation leading to the formation of polymer
with broader molecular weight range and poor
reproducibility. These inherent problems with in-
situ KCTP were overcome in 2008 by Kiriy and
coworkers wherein they reported the first synthe-
sis of rr-P3HTvia the ex-situ KCTP method.20-21
In this approach, the initiating species of the type
Ar-Ni[L2]-X were synthesized and isolated and
hence the term ex-situ initiation. Since there is no
formation of the intermediate “T-T” defective
dimer, ex-situ can in principle result in the syn-
thesis of defect-free rr-P3HT. Subsequently, dif-
ferent catalytic systems for ex-situ KCTP were
reported.22-30 Apart from the ability to produce
100% rr-P3HT, ex-situ KCTP also provided a
possibility to control the chain end functionalities
leading to rr-P3HT with complex molecular ar-
chitectures including surface grafting.22 An ex-
cellent and timely article by Kiriy and coworkers
reviewed the progress in this direction.31 One of
the major disadvantages with ex-situ KCTP has
been the complex synthetic strategy of initiating
species. The simplest initiating species reported
hitherto is by Nesterov and coworkers wherein
they reported single step synthesis of Ar-
Ni(dppp)-Br initiator using oxidative addition of
aryl halide to Ni(dppp)2.26 However the rate of
reaction for initiator synthesis was extremely
slow (48hr) with low yields (~50%). Further-
more, this approach is not versatile as it works
only with bithienyl halide and also Ni(dppp)2 is
not commercially available.
Based on the above discussion, it is clear that
there is a need for the development of alternative
synthetic strategies for the synthesis of simple,
stable and efficient initiating species for ex-situ
KCTP. Furthermore, if the catalyst can be made
soluble in the polymerization medium, batch-to-
batch reproducibility can be significantly im-
proved by employing continuous flow process.
In this manuscript we report a simple one pot
KCTP method for the synthesis of defect free rr-
P3HT via Ni(0) based ex-situ initiator. Some of
the other salient features of our approach are sta-
bility, solubility of the initiator, quantitative yield
(no purification) of the initiator, use of conven-
tional and commercially available Ni(II) catalyst,
large scale batch-to-batch reproducibility and
adaptability for continuous flow process. Urbach
energy calculations as well as solar cell device
studies were also carried out using this defect
free rr-P3HT.
RESULTS AND DISCUSSION
Ni(II) catalyzed KCTP is generally believed to
follow the similar catalytic cycle as other transi-
tion metal catalyzed C-C bond formation reac-
tions involving transmetallation, oxidative addi-
tion and reductive elimination as key steps.
However, KCTP differs significantly from other
catalytic cycles due to the inability to enter the
catalytic cycle using Ni(0) as it is unreactive to-
ward aryl halides.27,31-32 Interestingly, Nesterov
and coworkers showed that it is possible to do
oxidative addition of aryl halide with Ni(0) spe-
cies by judicious selection of more reactive aryl
halide such as based on bithiophene.26 Since
Kumada coupling is believed to undergo via the
Ni(0)species, it was decided to generate this spe-
cies using a sacrificial Grignard reagent to ex-
plore if the polymerization could result in the
formation of poly(3-hexylthiophene) as shown in
Scheme1. Interestingly, this resulted in the for-
mation of rr- P3HT.
2 eq i-PrMgX
Ph 2P
Ni
PPh 2 Ph 2P
Ni
PPh 2
Reductive
Ph 2P (0) PPh 2
Ni
THF Elimination
Cl Cl
Transmettalation
i-Pr i-Pr L L
rr-P3HT
C6H13
XMg S Br
Scheme 1 Ni(0) catalyzed synthesis of defect-
free rr-P3HT
In order to confirm the formation of Ni(0) specie,
we recorded the 31P NMR spectrum before the
addition of monomer (Figure 1) and it confirmed
the quantitative conversion of starting Ni(II) spe-
cies to Ni(0) on addition of two equivalent of
isopropyl magnesium chloride. This Ni(0) initiat-
ing species was found to be highly stable in solu-
tion even after 24h (Figure S5 of supplementary
information). Therefore, this can be easily pre-
pared and stored. However it should not be noted
that this Ni(0) specie is not stable against ambient
air and moisture and results in decomposition on
exposure. Therefore, all our efforts to isolate and
crystalize this Ni(0) specie were futile. Though
the exact nature of the specie is unknown at the
current juncture, its reproducibility (even at large
scale), ease of synthesis and ability to synthesize
defect free rr-P3HT have been proved beyond
any doubt as detailed later. Furthermore, the
conversion to generate this Ni(0) species is quan-
titative and hence no purification is needed which
is generally not the case with other ex-situ cata-
lysts.
Figure 1 31P NMR spectra in THF/CDCl3 of (a)
Ni(0) formed by the addition of two equivalent of
isopropylmagnesium chloride to Ni(dppp)Cl2; (b)
Ni(dppp)Cl2.
Hence, in a typical experiment, required amount
of Ni(dppp)Cl2 catalyst was suspended in dry
THF followed by slow addition of two equivalent
of isopropylmagnesium chloride resulting in a
clear greenish yellow solution. To this clear so-
lution was then added (in one portion) 100 mM
solution of the 2-bromo-3-hexyl-5-
thineylmagnesium chloride. This resulted in the
immediate formation of dark red/brown colour
solution, which was further stirred for 30 minutes
at room temperature. The final purified polymer
was obtained as thick film with green metallic
lustre. In order to confirm the pseudo living na-
ture of the polymerization, controlled polymeri-
zation experiments were carried out by varying
the ratio of monomer to catalyst and the results
are given in Table 1 and are represented graph-
ically in Figure S4 of supplementary information.
As expected, the polymerization follows a pseudo
living nature wherein the molecular weight can
be controlled by changing the ratio of the mono-
mer to catalyst.
We believe that the polymerization using this
Ni(0) species should follow the ex-situ polymeri-
zation mechanism wherein the first step will be
the oxidative addition of the monomer as shown
in Scheme 2. In general, the ex-situ polymeriza-
tion should result in the synthesis of defect-free
rr-P3HT if all the chains are initiated by the ex-
situ species coupled with absence of side reac-
tions such as disproportionation or chain transfer
reactions. In order to confirm the defect free na-
ture of the resulting polymer, MALDI and 1H
NMR analysis were carried out on a low molecu-
lar weight polymer (Entry 1, Table 1). As can be
seen from Scheme 2, for ex-situ polymerization,
all the chains should result in the formation of
polymer having hydrogen as one of the chain
ends (quenching of the thienyl magnesium halide
chain end). The other chain end could be hydro-
gen (should be major due to quenching of the liv-
ing nickel chain ends) or isopropyl (quenching of
the active chain end with unreacted isopropyl-
magnesium halide). For the quantification of
chain ends MALDI is proved to be the best tech-
nique and has been used by several research
groups.11, 27, 29 In fact the MALDI results confirm
these chain ends as shown in Figure 2. The peak
at 5323 g/mol corresponds to polymer with hy-
drogen as both chain ends (32n+H+H); and peak
at 5366 g/mol corresponds to polymer with hy-
drogen and isopropyl as chain ends (32n+H+i-
pr); and peak at 5402 g/mol corresponds to pol-
ymer with hydrogen and bromine as chain ends
(32n+H+Br). Very small fraction of the chain
ends contains hydrogen along with bromine as
chain ends. This could result from the chain ter-
mination due to the lack of oxidative addition of
Ni(0) to the terminal thienyl bromide propagating
chain end.
Table 1 Theoretical and experimental molecular weight as a function of monomerto catalyst ratioa

Catalyst Mn (kDa) Mn (kDa) Yield

Entry PDI
(mmol) Theoretical Experimentalb ( %)
1 1.66 10.0 9.2 1.2 82
2 1.11 15.0 14.2 1.2 84
3 0.55 30.2 26.2 1.5 79
4 0.3 50.4 51.8 1.5 78
5 0.21 79.2 74.0 1.6 75
6 1.43 11.6 10.0 1.1 80
7 0.3 50.4 50.8 1.4 75
8 0.3 50.4 52.0 1.5 78
a
All polymerizations were carried out using 100 mM monomer solution in THF at room temperature in
presence of four equivalent of lithium chloride. bMeasured by GPC in chloroform using polystyrene as
standard.

Figure 2 MALDI spectra of the defect free rr-

Scheme 2 Plausible ex-situ polymerization
mechanism for the synthesis of defect-free rr-
P3HT using Ni(0).
1
H NMR (Figure 3) further confirms the defect
free nature of the chains. NMR peak assign-
ments were done based on the analysis reported
by Senkovskyyet al. and Kohn et al.23, 29 The ab-
sence of two singlets of equal intensity at 6.86
and 6.93 confirm the absence of T-T defect at the
chain end group carrying bromine. Further, the
presence of two doublets at 7.16 and 6.93 ppm
(Chain end of H-T coupled rr-P3HT with hydro-
gen as chain end) confirms that all the chains are
initiated in ex-situ mode.
P3HT (Entry 1 of Table 1).
Therefore, we have conclusively shown that the
present method results in the synthesis of defect-
freerr-P3HT. As mentioned earlier, our initiating
species is soluble in polymerizing solvent, i.e.,
THF. This has implications, as soluble initiating
species enables one to carry out continuous flow
synthesis that provides better control over the
polymerization process and should result in pol-
ymers with narrow polydispersity due to efficient
mixing. It should be noted that continuous flow
synthesis of rr-P3HT has been reported earlier.33-
35
However all these methods use the traditional
in-situ GRIM method using Ni(II) as the catalyst.
Our initial attempts to carry out continuous flow
synthesis using this soluble ex-situ initiating spe-
cies (see supplementary information for detail)
resulted in the synthesis of defect free rr-P3HT
with number average molecular weight of 10kDa
and polydispersity of as low as 1.1 (Table 1, En-
try 6, see supplementary information for GPC). Figure 5 shows the lighted and dark J-V charac-
More work in this direction is currently under- teristic of organic solar cells fabricated using
way. Another advantage of the soluble initiating commercially available rr-P3HT and DF-P3HT
species is the better batch-to-batch reproducibil- donor polymers. Inverted structure
ity due to homogenous initiation resulting from ITO/ZnO/PEIE/P3HT:PCBM/MoO3/Ag was
mixing of two homogeneous solutions as com- used to fabricate these device. The solar cell pa-
pared to mixing of solid catalyst with monomer rameters of the best performing devices are
solution as is in case of traditional GRIM method summarized in the Table S1(Supplementary in-
using Ni(II). In order to demonstrate this, we formation). The solar cells fabricated using DF-
carried out relatively large-scale (at 300 g) syn- P3HT showed better performance (PCE=4.1%)
thesis of defect-free rr-P3HT with a target num- when compared to cells fabricated using rr-P3HT
ber average molecular weight of 50kDa and re- (PCE=3.7%). This increase in ca. 15% in PCE in
peated it (Table 1, Entry 7 and 8). As expected, DF-P3HT is mainly attributed to increase in the
the process is reproducible even at large-scale. Jsc and FF of DF-P3HT:PCBM cells. The in-
crease in Jsc and FF is due to better charge
transport properties which arises due to better
interchain ordering and better bimolecular pack-
ing of donor:acceptor molecules.29, 38
CDCl3
4
3
6
2 5 0
1 8 10
rr-P 3 H T
9 #
#
# # 7#
-2
E u = 38.5 m eV
10

A bs orba nc e
7.3 7.2 7.1 7.0 6.9 ppm 3.0 2.9 2.8 2.7 2.6 ppm
1.65
1.38
52.89
1.00

1.54
0.55
0.80
0.15
0.08

0
10
D F -P 3 H T

-2
10 E u = 35 m eV

7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
0 .8 1 .2 1 .6 2 .0 2 .4 2 .8 3 .2
E ne rg y ( e V )
1
Figure 3 H NMR spectra of the defect free rr-
P3HT (Entry 1 of Table 1). 13C satellite peaks are Figure 4 Absorbance as a function of photon en-
labeled by #. ergy of neat rr-P3HT and DF-P3HT films over
quarts substrate. The fitting of the Urbach tail is
Furthermore, to demonstrate the optoelectronic done using a linear equation to extract the Urbach
properties and application of defect-free rr-P3HT energy (Eu) of these films.
Urbach energy measurements were carried out
14
and organic solar cells were fabricated and char- D F -P 3 H T :P C B M
12
acterized. Urbach energy (Eu) of the polymers is rr-P 3 H T :P C B M

extracted from the absorption coefficient (α) of 10

J (m A /c m )

the material using the relation α(E) = αoexp(- 8

2

hυ/Eu), where hυ is the energy of the incident ex- 6

citation light. Figure 4 shows the plot of absorb- 4

ance with respect to light energy of neat rr-P3HT 2

film and DF-P3HT film. The Eu of DF-P3HT is 0

35 meV and that of rr-P3HT is 38.5 meV sug- -0.2 0.0 0.2 0.4 0.6
gesting less disorder present in DF-P3HT when B ia s (V )

compared to rr-P3HT film.36-37 This results veri-

Figure 5 J-V characteristic under AM 1.5 (solid)
fy the polymer quality; because of less PDI and
and dark (hollow) of P3HT:PCBM solar cells
high regioregularity which led to more order pol-
with ZnO and MoO3 as electron transport and
ymer chains in DF-P3HT polymer.
hole transport layer, respectively.

Single charge carrier devices were prepared with
the structure ITO/MoO3(15nm)/neat
P3HT(different thicknesses)/Au (50 nm) with
active layer consisting neat rr-P3HT and DF
P3HT of different thicknesses keeping the spin
parameter and annealing conditions same as that
of bipolar devices. We observed (Figure 6) that
the current density of DF P3HT(115 nm) at 1.5 V
as 11250 A/m2 whereas the rr P3HT(110 nm)
shows only 8553 A/m2.
10000
rr-P 3 H T
D F -P 3 H T
J (A /m )
2
1000
100
0 .0 0 .5 1 .0 1 .5
V olta g e (V )
Figure 6: J-V plot of hole only single charge car-
rier device fabricated using neat rr-P3HT and
DF-P3HT. ITO/MoO3/P3HT/Au structure was
used to fabricate hole only devices.
In summary, we have developed, for the first
time, a new initiating species for the one pot ex-
situ KCTP resulting in the synthesis of defect-
free rr-P3HT. The process is simple as it is based
on the commercially available catalyst. Further-
more, the conversion is quantitative (so no purifi-
cation required), initiating species is stable, solu-
ble and the process is amenable for continuous
flow synthesis. The novelty of the current ap-
proach is that we have used the same method as
used over the years for GRIM polymerization but
have changed the sequence of addition resulting
in the synthesis of defect-free P3HT. Therefore,
the present manuscript provides a significant ad-
vancement in the synthesis of defect-free rr-
P3HT. Our process resulted in the synthesis of
highly crystalline defect-free rr-P3HT that can
find interesting applications in various optoelec-
tronic devices which is proved by the Urbach en-
ergy calculations as well as solar cell device
studies. In addition to that, Hummelgen and co-
workers, studied the field effect mobilitiy (µFET)
of transistors and found µFET value of 1.2 cm2V-
1 -1
s for defect-free rr-P3HT.39 Furthermore, our
defect-free rr-P3HT polymer blended with
PC60BM provided optimal BHJ morphology to
get enhanced band-edge optical absorption and
charge transport properties, which leads to a high
performance OPV devices in comparison to
commercial rr-P3HT:PC60BM devices.40
ASSOCIATED CONTENT
Supporting Information. Experimental details,
GPC, NMR of high molecular weight polymer,
UV vis, DSC and solar cell fabrication and char-
acterization details are given in the supporting
information and this material is available free of
charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: anilkumar@iitb.ac.in.
2 .0
ACKNOWLEDGMENT
We thank DeiTy, MNRE and DST India for
financial support. DLT acknowledges UGC for
senior research fellowship. We also thank the
central facility of MALDI-TOF of IIT Bom-
bay. We acknowledge Ashok Kumar Majji for
NMR and MALDI studies.
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