Alternating arrays of different conjugated polymers utilizing a synthetic cross-linker

Article abstract of DOI:10.1002/chem.201002675

Exploring an approach to control the nanostructures of pconjugated polymers has been an important research target in materials science, which has led to the creation of various functional materials with optimized p-electronic properties.In particular, nan

Full text of DOI:10.1002/chem.201002675

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DOI: 10.1002/chem.201002675
Alternating Arrays of Different Conjugated Polymers Utilizing a Synthetic
Cross-Linker
Takahiro Kaseyama,[a, b, c] Rie Wakabayashi,[b] Seiji Shinkai,*[b] Kenji Kaneko,[d] and
Masayuki Takeuchi*[a, c]
Exploring an approach to control the nanostructures of p-
conjugated polymers has been an important research target
in materials science, which has led to the creation of various
functional materials with optimized p-electronic proper-
ties.[1] In particular, nanostructures of conjugated oligomer/
polymer blends have received growing interest in their ap-
plications, which include electronic devices such as field-
effect transistors, light-emitting diodes, photovoltaic cells.[2]
Several methods for controlling dimensionality, nanostruc-
ture, and morphology have been achieved through chemical
and physical techniques that utilize microphase separation,
layer-by-layer method, and so forth.[3,4] Supramolecular ap-
proaches also have been applied for the alignment and or-
ganization of conjugated oligomers and polymers in a non-
covalent manner, use of host matrix, liquid-crystalline phase,
air–water interface, and so forth.[5,6] From a supramolecular
point of view, we recently proposed a new approach toward
the alignment of conjugated polymers inspired by actin fila-
ment bundling proteins. A supramolecular cross-linking mol-
ecule (“aligner”), possessing conjugated polymer binding
sites, bundles and aligns them in a noncovalent fashion. The
concepts we have reported complement the existing tech-
niques for supramolecular and macromolecular assembly.
Introducing interactive sites for conjugated polymers at the
spacial position of the aligner molecules allows control over
the dimensions, morphologies, and interpolymer spacings.[7]
This approach basically permits the construction of alternat-
ing arrays of different conjugated polymers, which depends
upon the design of an aligner molecule displaying affinities
toward such polymers.
In this paper, we demonstrate that alternating arrays of
amino-functionalized conjugated polymer (CP) and polyani-
line emeraldine base (EB) were efficiently formed through
the supramolecular bundling of a synthetic cross-linker 1
(Scheme 1). Very interestingly, the morphologies of the re-
sultant conjugated polymer blends exhibited a well-regulat-
ed crystalline structure with periodicity of 2.0 nm. This ap-
proach can be regarded as a supramolecular two-dimension-
al polymerization of binary conjugated polymers. Compound
1 possesses two different binding sites which consist of cofa-
cial porphyrinatozinc complexes and two palladium com-
plexes. The former binding site was designed for recognizing
CP and the latter for EB through coordination bonds. These
binding sites are introduced around the terphenyl rotational
axis so that one binding event would afford positive influ-
ence on the subsequent binding event. We wanted to inte-
grate chromogenic groups so that we could confirm the
binding events between 1 and the conjugated polymers in
solution. When CP and EB are bundled and juxtaposed by
1, the distance between two polymers is calculated to be
2.0–2.3 nm in their energy-minimized states (see Supporting
Information, Figure S2). Given the structures of the two dif-
ferent polymers, CP and EB, one can envision that an ideal
alternative alignment only takes place at every “least
common multiple” distance of each repeating unit. We used
computational methods (Insight II, Discover) to evaluate
the pitch lengths of repeating units for CP and EB to be
about 1.4 and 1.9 nm, respectively. Given this difference,
[a] T. Kaseyama, Prof. M. Takeuchi
Macromolecules Group, Organic Nanomaterials Center
National Institute for Materials Science, 1-2-1 Sengen
Tsukuba, Ibaraki 305-0047 (Japan)
Fax : (+81)29-859-2101
Takeuchi.Masayuki@nims go.jp
[b] T. Kaseyama, Dr. R. Wakabayashi, Prof. S. Shinkai
Department of Chemistry and Biochemistry
Graduate School of Engineering, Kyushu University
744 Motooka, Nishi-ku, Fukuoka, 819-0395 (Japan)
E-mail: shinkai_center@mail.cstm.kyushu-u.ac.jp
[c] T. Kaseyama, Prof. M. Takeuchi
Department of Materials Science and Engineering
Graduate School of Pure and Applied Science, University of Tsukuba
1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571 (Japan)
[d] Prof. K. Kaneko
HVEM Laboratory, Kyushu University
744 Motooka, Nishi-ku, Fukuoka 819-0395 (Japan)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201002675.
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Scheme 1. a) Chemical structures of the aligner molecule 1, conjugated polymers (CP, EB) and their low molecular weight analogues (mEB, mCP) used
in this study. CP: number-average molecular mass (Mn)=26000; EB: Mn =20000. b) Schematic illustration of sequential bundling of conjugated poly-
mers with 1.
one can estimate that at every 5.6–5.7 nm a cross-linking
event will take place (every four repeating units for CP and
three repeating units for EB). Furthermore, a slight differ-
ence would be negligible due to the flexible benzyl ether-
type linkage inserted between terphenyl axis and binding
sites.[8] Compound 1 was synthesized according to Scheme
S1 (see Supporting Informa-
When only one of two palladium centers of one coordinated
to mEB, the absorption maximum of mEB should appeared
around at 686 nm as we already reported.[7d] These changes
and the e value at 790 nm are consistent with those of the
palladium complex-appended aligner–mEB system (Fig-
ure S11). In contrast, no spectral changes of porphyrinato-
tion)
and
identified
by
1H NMR, and MALDI TOF
MS spectroscopic evidence.
We first used mEB and mCP
as low molecular weight and re-
peating unit analogues of EB
and CP to carefully confirm
and evaluate the complexation
behaviors between EB and pal-
ladium complexes, and between
CP and porphyrinatozinc com-
plexes, respectively. The forma-
tion of the 1·mEB, 1·mCP, and
1·mEB·mCP complexes were
estimated from changes in the
UV/Vis
absorption
and
1H NMR spectra. Upon addi-
tion of mEB to a solution of 1
(88.0 mm) in chloroform/acetoni-
trile/tetrahydrofuran 9:1:1, we
observed the appearance of a
new band at 790.0 nm corre-
sponding to the complex forma-
tion wherein two imine sites of
mEB are coordinated by palla-
Figure 1. a) UV/Vis spectral changes of mEB upon addition of mEB (0–170 mm) in CHCl3/MeCN/THF 9:1:1 at
258C ([1]=88.0 mm). b) Plots of the absorbance at 790.0 nm of mEB (0–170.0 mm) vs. [mEB]/[1]. c) UV/Vis
spectral changes of 1·mEB (87.0 mm) complex upon addition of mCP (0–620.0 mm) in CHCl3/MeCN/THF 9:1:1
dium complexes (Figure 1a). at 258C. d) Schematic illustration of the 1·mEB·mCP complex.
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Arrays of Different Conjugated Polymers
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zinc complexes in 1 was observed, clearly showing that the
palladium complexes selectively bind mEB to afford 1·mEB.
The stoichiometry of the 1·mEB complex was estimated
from mole ratio plots to indicate the formation of a 1:1
[1·mEB] complex (Figure 1b). From analysis of the binding
isotherm using a non-linear curve fitting method prepared
from the UV/Vis absorption spectral changes of 1 (3.1 mm)
upon addition of mEB at 258C, we calculated the associa-
tion constant (KmEB/mÀ1) to be KmEB =2.8ꢁ105 (Figure S5).
In the case of porphyrinatozinc–mCP complexation, firstly
we confirmed that two porphyrinatozinc moieties of 1 do
not stack with each other under the conditions used in this
study; the lmax of the Soret band of 1 at 427 nm appeared at
the same wavelength as that of molecularly dispersed tetra-
kis[4-(2-ethylhexyloxy)phenyl]porphyrinatozinc. When com-
pound 1 (87.0 mm) was titrated with mCP in chloroform/ace-
tonitrile/tetrahydrofuran 9:1:1, bathochromic shift of the
Soret (to 430 nm) band and Q bands was observed, while no
chemical shift of the palladium complexes was observed in
the porphyrinatozinc–amine and the palladium complexes–
imine interactions can both be regarded as orthogonal for
the different polymer bundling.[9]
From foregoing findings, one can expect that the diimine
moieties in the repeating unit of EB and 1,4-bis(N-methyl-
aminomethyl)benzene moiety of CP would become recog-
nized by 1 and then become bundled. Indeed, spectral
changes upon addition of each of the polymers are similar
to those observed for 1·mEB and 1·mCP. The affinities
toward the repeating units of polymers appeared to be
almost the same as those for low molecular weight ana-
logues. The addition of 1 ([1]=0–87.0 mm) to a solution of
EB ([EBunit]=85.0 mm: [polymerunit] denotes the concentra-
tion of the repeating unit of polymer in Scheme 1a) resulted
in the bathochromic shifts of lmax of EB from 598.0 nm to
790.0 nm with broadening of the absorption band up to
1200 nm (Figure 2a). Judging from its high affinity toward
EBunit under the condition of [EBunit]/[1]=1, every EBunit
was recognized by the palladium complexes of 1 directing
the porphyrinatozinc moieties outside to form the n1·n-
1
the H NMR spectrum (Figure S3). These changes are con-
sistent with the zincporphyrinate–amine coordination
system and the association constant for 1:1 [1·mCP] complex
(KmCP/mÀ1) was evaluated to be KmCP =5.6ꢁ103 (Figures S6
and S7). This smaller KmCP in comparison with the previous-
ly reported values probably arises from interruption by the
tetrahydrofuran coordination to zinc. In fact, the KmCP value
of 1 and mEB in chloroform/acetonitrile was confirmed to
be 1.3ꢁ105 mÀ1 (Figure S8). We next measured the associa-
tion constant for tetrakis[4-(2-ethylhexyloxy)phenyl]por-
phyrinatozinc and mCP to be 870mÀ1 (Figure S4); in this
case the Soret band shifted from 427 to 432 nm. This associ-
ation constant is significantly smaller than that of 1·mCP, in-
dicating that two porphyrinatozinc of 1 should participate in
the binding of mCP. Foregoing findings clearly show that
palladium complexes in 1 have high affinity only toward
mEB and that the cofacial porphyrinatozinc moiety shows
moderate affinity only toward mCP under the conditions we
used here.
After the quantitative formation of 1·mEB ([1]=[mEB]=
87.0 mm), we successively added mCP to this solution. The
lmax values of the Q band (559.0 and 600.0 nm) of 1 shifted
to longer wavelengths (565.0 and 606.0 nm), while there was
no change in the lmax value of the 1·mEB complex at
790.0 nm with only a slight increase of its absorption. These
results show that 1 can interact both with mEB and mCP
without dissociation of each guest molecule (Figure 1c and
d). The association constant for the formation of
1·mEB·mCP from 1·mEB was calculated to be 5.5ꢁ103 mÀ1
(Figure S9). In a similar way, we evaluated the association
constant for the formation of 1·mEB·mCP from 1·mCP to
be 2.7ꢁ105 mÀ1. These values are almost the same as those
for KmEB and KmCP, supporting the view that the binding
event at one site does not provide a negative influence on
that at the other site (Scheme S2). We infer that the recogni-
tion-induced conformational changes in 1 at one site preor-
ganize the other site for the subsequent recognition; how-
ever, this effect is not so obvious in this system. In addition,
ACHTUNGNERT(NGNU EBunit) composite (Figure 2c,i). To this solution, we added
CP ([CPunit]=0–820 mm) to confirm if two polymers are rec-
ognized by 1 to form the polymer bundles, 1·EB·CP, in solu-
tion. Consequently the shifts of Q bands were also observed
without dissociation of EB and the changes became saturat-
ed when we mixed 800 mm of [CPunit] (Figure 2b and 2c,i).
Compound 1 thus cross-linked two different polymers and
bundled them in solution at this stage. Meanwhile, we con-
firmed from Vis/NIR spectral changes that 1·EB·CP assem-
blies are not efficiently formed either when we allow 1 to
complex with CP ([CPunit]/[1] 9.5:1) followed by the EB ad-
dition ([EBunit]/[1] 1:1) or when we add EB and CP simulta-
neously ([1]/ACHTUNRTGNEN[GU CPunit]/ACHTUTGNRNE[NGUN EBunit] 1:9.5:1). Given the degree of
polymerization of CP, each polymer chain of CP has about
forty CPunit on average, indicating that only three or four
sites of CPunit within a polymer chain are recognized by 1
under the conditions of [CPunit]/[1] 9.5:1 (Figure 2c,iii). From
such a 1·CP composite, the resultant 1·EB·CP was less
cross-linked by 1, as indicated by Vis/NIR spectral changes,
and eventually formed amorphous assemblies. In the case of
simultaneous addition of EB and CP solution, we could not
observe spectral changes of the Q bands of 1, probably due
to the unexpected CP–EB inter-polymer interaction in solu-
tion (Figure 2c,ii and Figure S16). Consequently, the
1·EB·CP assemblies formed through sequential organization
methods, depicted in Figure 2c,ii and iii, afforded amor-
phous assemblies rather than crystalline 2D structures (Fig-
ure S17).
Electron microscopic images of the resultant polymer as-
semblies cross-linked by 1 present information regarding
how two polymers are organized by 1 when they form crys-
talline assemblies. As confirmed by means of Vis/NIR spec-
troscopy, we prepared the 1·EB·CP assemblies through se-
quential organization of EB, then CP (Figure 2c,i) and ob-
tained solution–cast films on a TEM grid without staining.
The samples were subjected to TEM observation. Firstly we
confirmed that only compound 1, EB, CP, 1·CP and CP·EB
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M. Takeuchi, S. Shinkai et al.
mains containing ordered p-
stacked layers and the heaviest
atom, in this case Pd and Zn.
The energy dispersive X-ray
spectroscopic (EDX) study on
the 1·EB·CP assemblies indeed
revealed that the sheet struc-
ture contains Pd and Zn, al-
though we could not specify
spacial distribution of Pd, Zn,
and two polymers from EDX
analysis (Figure S15). As men-
tioned above, PdII and ZnII
atoms coordinated the imine
moieties in EB and the amine
moieties in CP, respectively;
therefore, EB and CP are prob-
ably ordered along these dark
contrast regions. It is notewor-
thy to emphasize that the dis-
tance of 2.0 nm is consistent
with the value which we calcu-
lated when EBs and CPs are
cross-linked by 1. From forego-
ing findings that the cross-
linker 1 bundled two different
Figure 2. a) Vis/NIR spectral changes of 1 (87.0 mm) upon addition of EB ([EBunit]=85.0 mm) in CHCl3/MeCN/
THF 9:1:1 at 258C. b) Absorption spectral changes of 1 upon addition of CP ([CPunit]=820 mm) to the solution
of a). c) Schematic illustration of the sequential organization of EB and CP.
form amorphous aggregates (Figures S12 and S13). In addi-
tion, intermediate composites of 1·EB ([EBunit]/[1] 1:1) were
mainly observed as amorphous agglomeration (Figure 3a).
Interestingly, when CP was added to the solution of 1·EB to
polymers in solution and the resultant crystalline assemblies
exhibited periodicity of 2.0 nm, we infer that EB and CP
were most likely alternatively bundled and aligned by 1
within the assemblies.
form 1·EB·CP assemblies ([1]/ACTHNURTGENNG[U CPunit]/ACHTUTGNERN[NUGN EBunit] 1:9.5:1), we
observed by means of TEM a folded 2D sheet structure
having dimensions greater than 1 mm2 (Figure 3b). Further-
more, over 80% of assemblies on the TEM grid displayed
sheet morphologies, they are indeed the main assemblies.
High cross-linking nature of this system would contribute
the formation of the sheet structure. The sheet structure
with clear electron-diffraction patterns is totally different
from that formed from 1, EB, CP, 1·EB or 1·CP (Figure 3c
and S14).
The 2D sheet structures were observed just after adding
the second polymer CP to 1·EB composite, suggesting that
the 2D sheets form instantaneously. We infer that this 2D
sheet could be kinetically metastable structure because after
a few days the precipitation started probably due to the
stack among 2D sheets. Figure 3d displays HRTEM images
of the 1·EB·CP assemblies in which the periodicity of the
multilamellar contrast was 2.0 nm, as determined from the
Fourier-filtered image. In the case of HRTEM measure-
ments, only when the aligned area is perpendicular to a
beam of electrons, can we observe the striped contrast, the
area of which is usually 100 nm square in this study. There-
fore the electron-diffraction pattern bears out the formation
of the crystalline supramolecular assemblies of conjugated
polymers, which were bundled by the synthetic cross-linker
1. Judging from the preceding data, darker sections in the
electron microscopic images of 1·EB·CP assemblies are do-
Figure 3. Electron microscopic images (no staining) of EB and CP
aligned by 1. a) TEM images of 1·EB assemblies ([EB]unit =85.0 mm and
[1]=83.0 mm). b) TEM image of 1·EB·CP assemblies ([EB]unit =85.0 mm,
[CP]unit =820 mm and [1]=83.0 mm). c) HRTEM images of 1·EB·CP as-
semblies. Inset: Electron diffraction pattern. d) HRTEM images of
1·EB·CP assemblies consisting of alternating dark and light stripes and
extracted periodical patterns from Fourier translation image. The perio-
dicity between the dark lines is 2.0 nm.
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Arrays of Different Conjugated Polymers
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Experimental Section
All starting materials and solvents were purchased from Tokyo Kasei
Chemicals or Wako Chemicals and used as received. The 1H NMR spec-
tra were recorded on a Bruker DRX 600 (600 MHz) spectrometer.
Chemical shifts were reported in ppm downfield from tetramethylsilane
as the internal standard. Mass spectral data were obtained using a Per-
ceptive Voyager RP MALDI TOF mass spectrometer and/or a JEOL
JMS HX110A high-resolution magnetic sector FAB mass spectrometer.
UV/Vis/NIR spectra were recorded using Shimadzu UV-2500 PC spectro-
photometers. Compound 1 was synthesized according to Scheme S1 in
Supporting Information.
TEM and HRTEM images were acquired using a JEOL TEM-2010 (ac-
celerating voltage: 120 kV) and a TECNAI-20 FEI (accelerating voltage:
200 kV), respectively. A sample solution was placed on a copper TEM
grid upon a holey carbon support film. The TEM grid was dried under
reduced pressure for 6 h prior to TEM observation.
Acknowledgements
M.T. and T.K. thank Dr. K. Sugiyasu of NIMS for valuable comments
and Mr. M. Frank for reading of the manuscript. This study was support-
ed partially by KAKENHI in a Priority Area “Super-Hierarchical Struc-
tures” (19022026 to M.T.) and on Innovative Areas (“coordination pro-
gramming”, Area 2107, 21108010 to M.T.) from the Ministry of Educa-
tion, Culture, Science, Sports, and Technology (Japan) . T.K. thanks the
JSPS for the Research Fellowship for Young Scientists for financial sup-
port.
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Keywords: alternating array
supramolecular chemistry
·
conjugated polymers
·
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Received: September 17, 2010
Published online: January 7, 2011
Chem. Eur. J. 2011, 17, 1793 – 1797
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
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