Supramolecular Graft Copolymerization of a Polyester by Guest-Selective Encapsulation of a Self-Assembled Capsule

Article abstract of DOI:10.1002/anie.201611394

Repeating guest units of polyesters poly-(R)-2 were selectively encapsulated by capsule 1(BF₄)₄to produce supramolecular graft polymers. The encapsulation of the guest units was confirmed by¹H NMR spectroscopy. The graft p

Full text of DOI:10.1002/anie.201611394

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International Edition: DOI: 10.1002/anie.201611394
German Edition: DOI: 10.1002/ange.201611394
Supramolecular Polymers
Supramolecular Graft Copolymerization of a Polyester by Guest-
Selective Encapsulation of a Self-Assembled Capsule
Yuta Tsunoda, Mei Takatsuka, Ryo Sekiya, and Takeharu Haino*
Abstract: Repeating guest units of polyesters poly-(R)-2 were
selectively encapsulated by capsule 1(BF4)4 to produce supra-
molecular graft polymers. The encapsulation of the guest units
self-assembled supramolecular capsules has not been
employed for the synthesis of graft copolymers.
It was previously shown that the resorcinarene-based
coordination capsule 1(BF4)4 encapsulates hydrogen-bonded
pairs of carboxylic acids and a variety of other molecular
guests within its nanosized cavity (Figure 1a).[16] The dissym-
metric nature of the capsule generates P and M enantiomers,
and a dynamic interconversion of these forms is permitted
due to the labile Ag+-N coordination (Figure 1b).[17] The
encapsulation of a chiral biphenyl guest (R)-G1 biases the
interconversion, which leads to the M form with an extremely
high diastereoselectivity of 98% de. We envisioned that such
a diastereoselective guest encapsulation could be applied in
the synthesis of a graft copolymer. Here, we report a novel
synthesis approach to introduce graft side chains onto
polymers poly-2a–d by site-selective encapsulation
(Scheme 1 and Figure 1d). The eight long alkyl chains of
the capsule were successfully grafted onto the polymer main
chains. Steric interactions between the grafted side chains
resulted in a conformational change of polyesters poly-(R)-
2a–d, which led to unique morphological transitions. The
chirality of a guest unit was efficiently transferred to the
helicity of the capsule, which induced a helical organization of
poly-(R)-2d and a chiral amplification of diastereoselective
encapsulation by the capsule.
1
was confirmed by H NMR spectroscopy. The graft polymer
structures were confirmed by the increase in the hydrodynamic
radii and the solution viscosities of the polyesters upon
complexation of the capsule. After the capsule was formed,
atomic force microscopy showed extension of the polyester
chains. The introduction of the graft chains onto poly-(R)-2
resulted in the main chain of the polymer having an M-helical
morphology. The complexation of copolymers poly-[(R)-2-co-
(S)-2] by the capsule gave rise to the unique chiral amplifica-
tion known as the majority-rules effect.
G
raft polymers are a unique class of block copolymers in
which one or more polymeric side chains are attached to each
repeating unit of a linear polymer backbone. Steric inter-
actions between the densely grafted side chains determine the
conformational flexibility of a linear polymer backbone,
which leads to extension of the main chain.[1] The physical
properties associated with the conformation of the main chain
can be controlled by varying the grafting density, which leads
to potential use in a wide-range of applications such as
photoresponsive polymer materials,[2] drug delivery,[3] and
nanomaterials.[4] Although covalent synthetic approaches—
“graft through,” “graft onto,” and “graft from”—have been
intensively studied for producing graft polymers,[5] multistep
synthesis methods are required to obtain graft polymers with
a high level of precision in their structure.[6]
Chiral guest polymers poly-(R)-2a–d were prepared by
acyclic diene metathesis (ADMET) polymerization.[18] Mon-
omers (R)-2a–d were subjected to a 2nd generation Grubbs
catalyst under the polymerization conditions described by
Schulz and Wagener.[19] The ADMET polymerization pro-
duced the corresponding polymers, poly-(R)-2a–d, with
number-average molecular weights that range from 16300
to 20900, which corresponded to degree of polymerization
(DP) values of 19–25 (Table 1).
Supramolecular polymer chemistry has become an active
research area in the field of polymer science,[7] and it offers
another option for the construction of graft polymers.
Pioneering work on supramolecular graft polymers was
reported for the development of liquid-crystalline materials.[8]
In addition, complementary multiple hydrogen-bonding
motifs were employed for the self-assembly of the side
chains of supramolecular graft polymers.[9] Molecular recog-
nition by pillar[n]arenes,[10] cyclodextrins,[11] cavitands,[12]
cucurbiturils,[13] and crown ethers[14] have been used for the
introduction of graft chains. Although many self-assembled
capsules have been developed,[15] molecular recognition by
Table 1: Characterization data for polyesters poly-(R)-2a–d.
[a]
Polymer
Mn [gmolÀ1 [a]
]
Mw/Mn
Yield [%]
DP
poly-(R)-2a
poly-(R)-2b
poly-(R)-2c
poly-(R)-2d
17000
20900
16300
17400
1.83
1.85
1.58
1.66
90
95
88
83
19
25
21
24
[a] Determined by size-exclusion chromatography.
[*] Y. Tsunoda, M. Takatsuka, Prof. Dr. R. Sekiya, Prof. Dr. T. Haino
Department of Chemistry, Graduate School of Science
Hiroshima University
Supramolecular grafting of poly-(R)-2a was carried out by
encapsulation in capsule 1(BF4)4. The encapsulation of a guest
unit was monitored by 1H NMR spectroscopy. Figure 2 shows
1-3-1 Kagamiyama, Higashi-Hiroshima, 739-8526 (Japan)
E-mail: haino@hiroshima-u.ac.jp
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
http://dx.doi.org/10.1002/anie.201611394.
1
the H NMR spectra of poly-(R)-2a in the presence of two
equivalents of 1(BF4)4. The acetoxymethyl resonance at d =
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Scheme 1. Schematic representation of supramolecular grafting directed by site-selective guest encapsulation in the self-assembled capsule
1(BF4)4.
apparent binding constants of the cap-
sule with the guest units were deter-
mined by competition experiments with
4,4’-diacetoxybiphenyl, which has a bind-
ing constant Ka of 82000 LmolÀ1.[16b]
Poly-(R)-2a–d showed fairly large bind-
ing constants of 33000, 26000, 24000,
and 55000 LmolÀ1, respectively.
Diffusion-ordered
spectroscopy
(DOSY) estimates the hydrodynamic
volume of a molecular aggregate in
solution.[20] DOSY experiments for poly-
mers poly-(R)-2a–d were carried out in
the presence of capsule 1(BF4)4. The
diffusion coefficients of the polymers
gradually decreased upon the addition of
the capsule (Figure 3a). Plots of the
diffusion coefficients versus degree of
encapsulation of the guest unit gener-
ated hyperbolic curves, which saturated
when more than 50% of the guest unit
was encapsulated. The relative hydro-
dynamic volume of the polymers can be
estimated from the diffusion coefficients.
The diffusion coefficient (D = 2.11 ꢀ
10À10 m2 sÀ1) of poly-(R)-2a reduced by
Figure 1. a) Self-assembled coordination capsule 1(BF4)4, b) schematic representation of dia-
stereoselective guest complexation to form G1ꢀ1(BF4)4, and the structures of c) monomers
(R)-2a–d and d) polymers poly-(R)-2a–d.
2.3 ppm moved to a clear window upfield of d = 0 ppm
(Figure 2b).[16a,b] The individual signals of the bound and
unbound guest units could be observed at ambient temper-
ature, which supports the idea that a sizeable kinetic barrier
exists during the in-and-out exchange process of a guest unit
in the capsule. The large complexation-induced shift (CIS) of
Dd = À3.53 ppm for the acetoxymethyl signal clearly indi-
cates that these groups are located in a strong shielding
region, which is provided by the resorcinarene cavities that
are walled by the eight aromatic rings of the cavitands. Thus,
the primary axis of each guest unit is located along the C4 axis
of the capsule (Figure 1b). The dominant acetoxymethyl
signal of the bound guest unit appeared at d = À1.22 ppm
together with minor signals, and this demonstrates the
diastereoselective formation of diastereomeric complexes.[17]
Guest units of polymers poly-(R)-2a–d were also encapsu-
lated by the capsule in a diastereoselective fashion. The
38% when the degree of encapsulation of the guest unit
approached 81%. Assuming that all the polymers are hydro-
spherical, the hydrodynamic volumes of the polymers are 14–
15 times larger than those of the polymers without the
capsule. These results suggest that the grafting of side
chains by guest encapsulation appreciably expands the
polymer structures in solution. This structural expansion
influenced the viscosity of the polymer in solution.[21] Specific
viscosities (hsp) of the polymers were determined with and
without 1(BF4)4 (Figure 3b). The specific viscosities of poly-
(R)-2a–d exhibited a good linear correlation with the polymer
concentration. The addition of the capsule to the solution of
poly-(R)-2a–d resulted in an increase in the specific viscos-
ities and the generation of curved plots. The clear difference
in viscosity is evidence that the graft chains are noncovalently
bound to the polymer main chains.
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Figure 2. 1H NMR spectra of poly-(R)-2a (0.053 mmolLÀ1), poly-(R)-2a
(0.053 mmolLÀ1) with 1(BF4)4 (2.0 mmolLÀ1), and 1(BF4)4
(2.0 mmolLÀ1) in CDCl3 at 298 K.
Figure 3. a) Plots of diffusion coefficients (D) versus the degree of
encapsulation of the guest units of poly-(R)-2 (0.43 mmolLÀ1; 2a:
*
,
Figure 4. AFM topographic images of a–c) poly-(R)-2a and d–f) poly-
~
^
2b: &, 2c: , 2d: ) with 1(BF4)4 in CDCl3 at 298 K. b) Specific
(R)-2d without 1(BF4)4 (a,d), with 0.5 equiv 1(BF4)4 per guest unit
(b,e), with 1.5 equiv 1(BF4)4 per guest unit (c), and 3.0 equiv of 1(BF4)4
per guest unit (f) on mica. The sizes of the images are (a–d)
1 mmꢀ1 mm, and (e,f) 500 nmꢀ500 nm.
~
*
^
viscosities (hsp) of poly-(R)-2a–d (2a: , 2b: &, 2c: , 2d: ) without
~
&
*
1(BF4)4 and with 1.5 equiv 1(BF4)4 per guest unit (2a: , 2b: , 2c:
,
^
2d: ) in CDCl3 at 298 K.
AFM measurements showed the conformational changes
of poly-(R)-2a upon the grafting of capsule 1(BF4)4
(Figure 4). The polymers without the capsule were arranged
in random aggregates (Figure 4a). Fibrillar morphologies of
poly-(R)-2a were formed in the presence of the capsule
(Figure 4b,c). As the concentration of the capsule increased,
the chain extension became apparent. These results indicate
that the sterically bulky capsules located on the polymer main
chain most likely generate significant steric interactions with
neighboring capsules; as a result, the polymer main chain
loses its conformational flexibility, which results in main-
chain extension. The lengths of the polymer chains were
roughly measured from Figure 4c to be (101 Æ 10) nm,
compared to a length of 4.4 nm for monomer (R)-2a,
obtained from a molecular modeling study conducted using
MacroModel V9.1.[22] The DP of poly-(R)-2a grafted with the
capsule was calculated to be 23, which moderately coincides
with the observed DP of 19. More apparent morphological
differences were observed in the AFM images of poly-(R)-2d
in the absence and presence of the capsule. Poly-(R)-2d was
found to have a random aggregation (Figure 4d). When
0.5 equiv of the capsule was added to the polymer solution,
widespread polymer networks were formed (Figure 4e).
Further addition of the capsule surprisingly produced helical
morphologies, with the M-helical configuration being domi-
nant with an average pitch of (15 Æ 1) nm (Figure 4 f). The
presence of the capsule on the polymer chains caused the
intermolecular steric interactions between the bound capsules
that resulted in a helical morphology.
Induced circular dichroism (CD) was observed when
optically active guest units with the R configuration were
encapsulated within the cavity. An intense absorption of a p-
p* transition in the bipyridyl unit was observed at l = 310 nm
(Figure 5). The addition of poly-(R)-2a resulted in induced
plus-to-minus bisignate CD signals of 1(BF4)4 emerging at l =
328 and 270 nm, which indicates that the helical interconver-
sion of 1(BF4)4 is biased. It is known that the plus-to-minus
CD signals are characteristic of the M configuration, which
becomes dominant in the helical interconversion of 1-
(BF4)4.[17a]
Majority-rules experiments demonstrated a unique chiral
amplification in the supramolecular graft polymers. Copoly-
mers poly-[(R)-2a–d-co-(S)-2a–d] were prepared to examine
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In conclusion, we have demonstrated the synthesis of
supramolecular graft copolymers by guest encapsulation by
a self-assembled chiral capsule. The formation of the graft
polymers in solution was demonstrated by an upfield shift of
the acetoxymethyl resonance, a decrease in the diffusion
coefficient, and an increase in the specific viscosity. The
introduction of the graft chains resulted in unique morpho-
logical changes in the solid state. AFM images confirmed the
extended chain structures and the helical chain structures,
which were directed through intermolecular steric interac-
tions between the grafted capsules. The chiral guest units of
the copolymers determined the helicity of the capsule in
solution. The bound capsule was sterically linked to the
others, which resulted in a unique chiral amplification known
as the majority-rules effect. This study demonstrates that the
formation of self-assembled capsules provides a unique
method for constructing graft copolymer structures in a non-
covalent fashion.
Figure 5. Left: Circular dichroism spectra of 1(BF4)4 (9.0ꢀ10À5 molLÀ1
in the presence of poly-(R)-2a (a–h: [guest unit]=0.0, 4.5, 9.0, 13.5,
)
18.0, 27.0, 36.0, 45.0ꢀ10À5 molLÀ1), and UV/Vis absorption spectra of
1(BF4)4 (i) and poly-(R)-2d (j) in chloroform at 298 K. Right: Normal-
ized CD intensities of 1(BF4)4 (9.0ꢀ10À5 molLÀ1) in the presence of
copolymers poly-[{(R)-2a–d}x-co-{(S)-2a–d}1Àx] (x=0.500, 0.675, 0.750,
0.875, and 1.000) ([guest unit]=45.0ꢀ10À5 molLÀ1) (poly-2a: , poly-
*
~
^
2b: &, poly-2c: , poly-2d: ). Error bars denote standard errors of
the means.
the chiral amplification behaviors. The good linear correla-
tion between the normalized CD intensities of copolymers
poly-[(R)-2a–d-co-(S)-2a–d] and their enantiomeric excess
indicates that the majority-rules effect is not operative in
these polymerization processes (Figure S40). When copoly-
mers poly-[(R)-2a–c-co-(S)-2a–c] were added to the solution
of capsule 1(BF4)4, the CD intensities of the capsule were
linearly correlated with the enantiomeric excess of the
polymers (Figure 5). No chiral amplification was observed
in the complexation of the capsule with copolymers poly-[(R)-
2a–c-co-(S)-2a–c]; therefore, the guest chirality is independ-
ently transferred to the helicity of the capsule. In contrast, the
complexation of poly-[(R)-2d-co-(S)-2d] to the capsule
showed a remarkable deviation from linearity, which indicates
that the enantiomer in excess had a disproportionate effect on
the helicity of the capsule bound to the polymer main chains.
This chiral amplification is clearly associated with the distance
between guests. When multiple guest units are encapsulated
by the capsule, the bound capsules come closer to each other
on the polymer chain. Although the R-configured guest unit
directs the favorable M helicity of the capsule, the favorable
subordinate P helicity of the capsule with a S-configured
guest unit was biased to the unfavorable predominant
M helicity of the capsule with an S-configured guest unit
(Figure 6). The energetic penalty of the unfavorable diaste-
reomeric complex (S)-guest unitꢀ(M)-1 is most likely com-
pensated by the preferable steric interaction at the exteriors
of the neighboring predominant diastereomeric complex (R)-
guestꢀ(M)-1.
Acknowledgements
This work was supported by JSPS KAKENHI Grant Num-
bers JP24350060, JP15H03817, JP15H00946, and JP15H00752
and was partially supported by the Platform Project for
Supporting Drug Discovery and Life Science Research
(Platform for Dynamic Approaches to Living System) from
the Japan Agency for Medical Research and Development
(AMED).
Conflict of interest
The authors declare no conflict of interest.
Keywords: chiral amplification · majority rules · polymers ·
supramolecular chemistry
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Manuscript received: November 21, 2016
Final Article published: && &&, &&&&
6
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ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2017, 56, 1 – 7
These are not the final page numbers!

Angewandte
Communications
Chemie
Communications
Supramolecular Polymers
Guest of honor: Repeating guest units of
polyesters were selectively encapsulated
in a self-assembled capsule to produce
supramolecular graft copolymers with an
induced M-helical morphology. A unique
chiral amplification was observed in the
molecular recognition of the capsule,
which is known as the majority-rules
effect.
Y. Tsunoda, M. Takatsuka, R. Sekiya,
T. Haino*
&&& — &&&
Supramolecular Graft Copolymerization
of a Polyester by Guest-Selective
Encapsulation of a Self-Assembled
Capsule
Angew. Chem. Int. Ed. 2017, 56, 1 – 7
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
7
These are not the final page numbers!