Finely Controlled Circularly Polarized Luminescence of a Mechano-Responsive Supramolecular Polymer

Article abstract of DOI:10.1002/anie.201911380

Finely controlled circularly polarized luminescence (CPL) supramolecular polymerization based on a tetraphenylethene core with four l- or d-alanine branch side chains (l-1 and d-1) in the solution state is presented, resulting from the tuning of mechanica

Full text of DOI:10.1002/anie.201911380

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Accepted Article
Title: Finely Controlled Circularly Polarized Luminescence of a
Mechano-Responsive Supramolecular Polymer
Authors: Seonae Lee, Ka Young Kim, Sung Ho Jung, Ji Ha Lee,
Mihoko Yamada, Ramarani Sethy, Tsuyoshi Kawai, and Jong
Hwa Jung
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201911380
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Finely Controlled Circularly Polarized Luminescence of a
Mechano-Responsive Supramolecular Polymer
Seonae Lee,[a],† Ka Young Kim,[a],† Sung Ho Jung, Ji Ha Lee, Mihoko Yamada, Ramarani Sethy,
[b]
[c]
[d]
[d]
,
[d]
,[a]
Tsuyoshi Kawai,* and Jong Hwa Jung*
Abstract: We report on finely controlled circularly polarized
luminescence (CPL) supramolecular polymerization based on a
tetraphenylethene core with four L- or D-alanine branch side chains
mechanical stimulus triggers transitions between several
crystalline and amorphous phases or between an aggregated and
a monomeric state, which are responsible for changes in the
luminescence emission.[
19-25]
Although mechano-responsive
(L-1 and D-1) in the solution state resulting from the tuning of
materials have been developed for mechanical stress sensing[
and security tag applications,[21] owing to the limit of expression of
both chirality and luminescence properties, mechano-responsive
materials that enable control of CPL characteristics have been
only two studies reported by Kawai[24] and Yamashita[25] groups.
In previous studies, the researchers have reported the control of
chirality in hydrogels composed of two components and a
luminescence dissymmetry factor of two difluoro-boron-β-
diketonate complexes. In contrast, the kinetically controlled
mechano-responsive chiral supramolecular polymerization
through the control of CPL property has not been reported,
despite their benefits as the seed and building block in living
supramolecular co-polymerizations. Therefore, the investigation
of CPL supramolecular polymerization generated by a finely
tuned external stimulus (e.g., rotation, pressure, and light) still
remains a significant challenge. Here, we report on kinetic
controlled CPL supramolecular polymerization with four L- or D-
alanine branch side chains formed by the fine-tuning of a
mechanical stimulus. Interestingly, CD and CPL signals were able
to be finely tuned by controlling rotational speed; increasing the
rotational speed led to the acceleration of a large enhancement
of CD and CPL signals.
20]
mechanical stimulus. Weak, green emissions of L-1 and D-1 in
tetrahydrofuran (THF) were converted to strong blue emissions by
tuning the mechanical stimulus. The strong blue emissions were
caused by an aggregation-induced emission (AIE) effect during the
formation of
a
supramolecular polymer. Lag time in the
supramolecular polymerization was drastically reduced by the
mechanical stimulus, which was indicative of the acceleration of the
supramolecular
polymerization.
Interestingly,
a
significant
enhancement of circular dichroism (CD) and CPL signals of the L-1
and D-1 was observed by tuning the rotational speed of the
mechanical stimulus, which implies that the chiral supramolecular
polymerization was accelerated by the mechanical stimulus. These
results imply that the CPL signals were tuned by the strength of the
external mechanical stimulus.
Circularly polarized luminescence (CPL) is a unique chiroptical
property of chiral emission systems and regarded as one of the
most important tools for investigating the excited-state properties
of chiral materials.[1-15] Materials exhibiting CPL are of great
interest not only for understanding the mystery of chirality but also
for potential important applications, such as chiroptical
recognition sensors,[8,9] noninvasive biomedical diagnosis in the
biological field,[10-13] and catalysts for asymmetric chemical
synthesis.[14,15]
Mechano-responsive materials also usually exhibit emission
properties under mechanical stress.[16-18] In most cases, this effect
results from the formation of supramolecular nanostructures;
[a]
S. Lee,[†] Dr. K. Y. Kim,[†] Prof. J. H. Jung
Department of Chemistry and Research Institute of Natural
Sciences
Our molecules L-1, D-1 and 2 were designed using a typical
strategy utilized in the study of supramolecular polymers based
on tetraphenylethene molecule bearing hydrogen-bonding
moieties and long alkyl chains. In particular, a tetraphenylethene
core of L-1 and D-1 in the supramolecular polymers was
introduced due to unique aggregation-induced emission (AIE)
characteristics with the external stimulus. L-1 and D-1 were also
expected to helically self-assemble through the CH-π stacking of
tetraphenylethene planes and the intermolecular hydrogen
bonding of amide groups. Compound 2 was prepared as a
reference to the essential role of chiral moiety in CPL
supramolecular polymerization.
Gyeongsang National University
Jinju, 52828 (Republic of Korea)
E-mail: jonghwa@gnu.ac.kr.
Prof. S. H. Jung
Department of Liberal Arts
Gyeongnam National University of Science and
Technology(GNTECH),
Jinju, (Republic of Korea)
Dr. J. H. Lee
Department of Chemistry and Biochemistry
University of Kitakyushu
[
b]
[
c]
d]
Hibikino, Kitakyushu 808-0135, Japan
Dr. M. Yamada, Dr. R. Sethy, Prof. T. Kawai
Division of Materials Science
[
Nara Institute of Science and Technology, NAIST
The absorption and luminescence spectra of L-1, D-1 and 2
were first observed using a constant clockwise rotational speed in
tetrahydrofuran (THF). As shown in Figure S1A, the maximal
absorption band was located at 333 nm in the THF without stirring.
The absorption band slowly shifted to 338 nm for 4.5 h. In contrast,
8916-5 Takayama, Ikoma, Nara 630-0192, Japan
[†
]
These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of
the document
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interestingly, the maximal absorption band of L-1 at 333 nm in the
THF rapidly shifted to 338 nm, within one isosbestic point, by
tuning the rotational speed from 200 to 1,000 rpm (Figure S1B).
These absorbance changes were dependent on the clockwise
rotational speed, and the spectral changes suggested that
monomeric molecules of L-1 with twisted conformation were
quantitatively converted to the supramolecular polymer by tuning
the mechanical stimulus.
the rotation speed was 1,000 rpm. This was attributed to the
formation of the supramolecular polymer via the intermolecular
hydrogen-bonding interaction by the dissociation of the
intramolecular hydrogen-bond formed in the monomer L-1 by the
mechanical stimulus. These findings indicate that the external
mechanical
stimulus
accelerated
the
supramolecular
polymerization, which is the first example of supramolecular
polymerization promoted with a mechanical stimulus. In addition,
we observed a change in the luminescence spectra depending on
the sample concentration, stirrer size, and vial size (Figures S3–
S5). The increase in luminescence intensity at 455 nm was
accelerated depending on the concentration of L-1. In contrast,
the stirrer size with a constant vial diameter and the vial size did
not affect the changes in luminescence spectra (See SI, explained
in detail).
Scheme 1. Mechanism of supramolecular polymerization of L-1 and D-1; (a)
monomeric species, (b) the formation of linear nanorod, and (c) chiral
supramolecular polymers with left- or right handed helicity by mechanical stimuli.
Figure 1. (A) Luminescence spectra of (a) green and (b) blue L-1 (2.5 × 10-5 M)
in THF. (B) Plot for luminescence intensity of L-1 obtained by different rotational
speeds at 455nm vs time.
Since L-1 and D-1 have a chiral center localized at the alanine
moieties, we measured their CD spectra to study the
supramolecular chirality (Figures S6, S7, and S8). An L-1 weak
positive CD signal at 325 nm was obtained without rotation, which
corresponded to the π-π* transition of the L-1 tetraphenylethene
moiety. A distinct and drastic enhancement of the CD signal for
the negative sign at 275 nm and the positive sign at 325 nm was
observed, which was ascribed to the formation of a left-handed
In addition, a L-1 broad, green and weak emission band was
obtained without rotation at 500 nm (λex = 333 nm) in the THF
(
Figure 1A). Interestingly, the luminescence spectrum of L-1
shifted to 455 nm over time, and the emission color changed from
green to blue. The luminescence intensity of L-1 at 455 nm was
~500-fold higher than that exhibited by the green emission. This
intense enhancement of the luminescence intensity was due to
the AIE effect in the formation of the supramolecular polymer. This
AIE effect with the blue emission was due to a larger torsion angle
(
M-type) supramolecular polymer characterized by excitonically-
[
28]
coupled helical organization. In contrast, the CD signal of D-1
was exactly the opposite behavior of L-1 (Figures S6B, and S8).
This CD signal of D-1 indicates that the tetraphenylethene moiety
was orientated in the right-handed (P-type) direction. The
enhancement of the CD signal of D-1 by the mechanical stimulus
showed the same tendency as L-1, suggesting that the
supramolecular chirality induced by the mechanical stimulus was
dominated by a stereo-enantiomeric residue. In addition, the CD
intensity of L-1 and D-1 was not significantly changed without
stirring until 600 min (Figure S6B). In contrast, the CD intensity of
L-1 and D-1 linearly increased by rotation at 1,000 rpm and
maintained a constant intensity after 240 min (Figure S6B), which
indicates that the supramolecular polymerization was accelerated
and supramolecular helicity was induced only by the mechanical
stimulus. The enhancement of the distinct CD intensity also
depended on the rotation speed (Figures S7 and S8). Based on
and
tetraphenylethenes.
spectral changes at various clockwise rotation speeds (i.e. 200,
00, 600, 800, and 1,000 rpm) (Figures S2 and 1B). Interestingly,
a plot of the luminescence intensity at 455 nm as a function of
time shows typical sigmodal curve characterized by
nucleation-elongation mechanism with lag time when a solution of
L-1 was maintained without rotation. This long lag time was due
to the presence of an intramolecular hydrogen-bond between the
amide groups of the alanine moieties in L-1, which restricted the
rapid growth of the supramolecular polymer.[27] The lag time in the
supramolecular polymerization was drastically reduced by
increasing the rotation speed, and the luminescence intensity
reached a maximum within 90-155 min (Figure 1B). The weak
green emission was rapidly converted to a blue emission when
a
more
twisted
conformation
and
stacking
[
26]
Therefore, we observed luminescence
4
a
a
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the luminescence and CD observations, we realized that the
mechanical stimulus of solution L-1 and D-1 generated not only
strong luminescence with an AIE effect but also chiral
supramolecular polymerization, which is a rare example of
supramolecular polymerization (Scheme 1). Especifically, on the
basis of luminescence and CD observations, the lag time in the
min of rotation (Figures 2b and S11). After stirring the solution for
120 min, the long fiber-like structure with clear left-handed helicity
was observed. More interestingly, the fiber lengths were
controlled by rotational time (Figure S11), which was the first
example for the control of fiber length by rotational times. These
findings suggest that the degree of polymerization can be
CD observation was longer than that of luminescence observation. controlled by external mechanical stimulus. Thus, the fiber tuned
A linear nanorod, which exhibits luminescence with an AIE effect,
was formed. However, the molecules in the nanorod were not
arranged helically in the initial state. After a certain mechanical
stimulus, the nanorod grew into the fiber structure. In this process,
the linear molecular arrangement in the nanorod was converted
into the helical molecular arrangement during the formation of the
fiber structure by mechanical stimulus. Thus, external mechanical
stimulus acted as a helical inducer and accelerator during
supramolecular polymerization.
by mechanical stimulus is useful as seed and building block in
living supramolecular block copolymerization. In contrast, the
AFM image of D-1 with a blue emission showed a right-handed
helical fiber (Figure S12). These observations suggest that the
fiber-like structure of the supramolecular polymer with blue
emission was generated by a nucleation-elongation mechanism,
as demonstrated by the time and temperature dependent CD
spectral changes (Figures 1B and S13). Furthermore,
interestingly, the length of the supramolecular fibers was
shortened by the mechanical stimuli strength increased at the
same luminescence intensity (I = 500), which indicates that the
supramolecular polymerization was accelerated by the rapid and
more nucleation formation in solution by increasing mechanical
strength. (Figure S14). Additionally, the ~70 nm diameter left-
handed (M-type) fibers were obtained by anticlockwise rotation
To investigate the influence of rotation direction on the
handedness and the AIE effects, we observed the luminescence
and CD spectral enhancements of L-1 under anticlockwise
rotation (Figure S9). The resulting enhancement of the L-1
luminescence was exactly the same obtained from the clockwise
rotation. This observation was opposite to that previously reported
in the literature,[25,29-31] in which supramolecular helicity was
controlled by rotation direction. In previous studies,[25,31-33]
researchers investigated the control of helicity of achiral
compounds by the rotational direction. The helicity of achiral
compounds depended on the rotational direction. However, the
helicity of L-1 at the supramolecular level was independent of the
stirring direction owing to the chiral alanine moiety. External
stimulus is not sufficient to invert helicity to original chirality owing
to the steric hindrance effect of the chiral center. Thus, molecular
chirality was directly reflected on supramolecular helicity.
(
Figure S15). This result again confirms that the handedness of
the supramolecular polymer L-1 was not determined by the
external stimulus-like rotation direction.
As a reference experiment, we observed the luminescence
spectral change of 2 composed of glycine moieties instead of
alanine moieties under the same condition (Figure S10A). The
weak emission band of 2 (2.5 × 10−5 M) was also obtained at 500
nm in the THF without stirring. However, the green emission band
did not change to a blue emission even though solution 2 was
under strong rotation (1,000 rpm) for 7 days (Figure S10B). These
findings indicate that the enantiomeric alanine moiety of L-1 and
D-1 plays a critical role in the conversion of the monomer to the
chiral supramolecular polymer with
a helical arrangement.
-
5
Because the intramolecular hydrogen bonds of L-1 and D-1 were
easily dissociated by the structural steric hindrance owing to the
presence of methyl groups. Then, non-intramolecular hydrogen-
bonded monomers L-1 or D-1 grew into CPL supramolecular
polymers in the chiral direction of alanine by intermolecular
hydrogen bonding.
Figure 2. Time dependent AFM images of L-1 (2.5ⅹ10 M) in THF; (a) 20 min,
(
b) 60 min, (c) 120 min, and (d) 240 min under 1,000 rpm.
1H NMR spectra changes of L-1 by change of temperature
were observed (Figure S16). Two N-H proton peaks of L-1 with
blue emission, prepared by stirring for 1 day, were observed at
To gain an insight into the morphological changes of the self-
assemblies over the time of mechanical stimulation, we observed
the morphologies of supramolecular polymers L-1 and D-1 using
atomic force microscopy (AFM, Figures 2 and S11–12). The AFM
image of L-1 with a green emission could not be clearly obtained.
However, the AFM image of L-1 with a blue emission, obtained at
a rotational speed of 1,000 rpm showed the nanorod-like structure
with uniform length of ca. 0.3 μm after 20 min of rotation (Figures
7.79 and 7.64 ppm at 298 K, respectively, which were shifted 0.16
and 0.17 ppm downfield compared to those at 333 K. These
chemical shifts were clear evidence for the dissociation of the
intermolecular H-bonds (See SI: explained in detail). In addition,
the -NH of L-1 with green emission showed bands at 3583 and
3
507 cm−1 and 2 showed bands at 3550 and 3482 cm−1,
respectively (Figure S17), which corresponds to the non-
hydrogen-bonded and intramolecular hydrogen-bonded -NH
groups. In contrast, the -NH band of L-1 with blue emission shifted
2a and S11), and was observed a short fiber-like structure with
uniform length of ca. 0.8 μm and a diameter of ~70 nm after 60
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−
1
to 3294 cm , which was indicative of the formation of
intermolecular hydrogen-bonding interactions between the amide
groups of L-1. This is clear evidence that the mechanical stimulus
accelerated the chiral supramolecular polymerization by the
dissociation of the intramolecular hydrogen-bonds through the
formation of intermolecular hydrogen-bonds.[32,33]
alanine moieties by tuning the rotational speed. The dissymmetry
factors (|glum|) of the CPL signals of L-1 (D-1) were successfully
controlled by the external mechanical stimulus; this is the first
example of the control of the dissymmetry factor of the CPL
signals. The molecules exhibited tunable emission by changing
from green to blue in solution. The chiral supramolecular polymers
exhibiting the blue emission by AIE effect were generated by a
typical nucleation-elongation pathway. More interestingly, the
important enhancement of the CD and CPL signals in the L-1 and
D-1 solutions was observed when the external stimulus was used
compared with when it was not used, to reach high dissymmetry
−
2
(
|glum|) values of ±2.2 × 10 under a rotational speed of 1,000 rpm.
Furthermore, the CD and CPL signals were able to be finely tuned
using different strengths and durations of the external mechanical
stimulus. Therefore, we believe that this unique mechano-
responsive CPL will provide a distinctive insight into the design of
functional chiroptical living supramolecular polymers based on
emissive chiral molecules.
Figure 3. (A) Time dependent CPL spectra of L-1 (blue line) and D-1 (red line)
-
5
(2.5ⅹ10 M) with 1,000 rpm in THF. (B) Plot of time dependent glum factor of L-
1
and D-1 with 1,000 rpm at 455 nm in THF; (a) 1,000, (b) 600, (c) 200, (d) 0
rpm for L-1 (positive signals) and D-1 (negative signals), respectively.
Acknowledgements
We then studied the effects of mechanical stimulus on the CPL
properties using different rotation rates (i.e. 200, 600, and 1,000
rpm) under the same solvent conditions as the CD observations,
namely a mechano-CPL effect. The changes in the CPL spectra
of both L-1 and D-1 at different rotational speeds are presented in
Figures 3 and S18–19. The mirror-image CPL signals for the two
enantiomers at 455 nm at the same rotation rate of 1,000 rpm
were observed in the L-1 and D-1 samples. The helicity of the CPL
signals were the same as the CD signals, which indicates that the
CPL helicity of the supramolecular polymers originated from the
molecular chirality localized at the alanine moiety. More
interestingly, very weak CPL signals changes of L-1 and D-1 were
observed during stirring in the initial stage (Figure S19), which
were ascribed to the intramolecular hydrogen-bonds of L-1 and
D-1. However, the CPL signals of L-1 and D-1 increased almost
linearly after a constant rotational time, as shown by the CD
observations, and the maximum CPL signals were dependent to
the rotational speed. These findings suggested that the well-
ordered helical molecular arrangement of L-1 and D-1 molecules
in the chiral supramolecular polymerization was controlled by the
mechanical stimulus. The magnitude of the CPL can be evaluated
by the luminescence dissymmetry factor (|glum|), which is defined
This work was supported by
a
grant from NRF
(
2017R1A4A1014595 and 2018R1A2B2003637). In addition, this
work was partially supported by a grant from the Next Generation
BioGreen 21 Program (SSAC, grant no. PJ013186052019), Rural
development Administration, Korea.
Keywords:
•
Supramolecular Polymerization
•
Circularly
Polarized Luminescence • Helicity • AIE Effect • Mechano-
Responsive Material
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5
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COMMUNICATION
Controlled Circularly Polarized
Luminescence: These results
imply that the CPL signals were
tuned by the strength of the
S. Lee, K. Y. Kim, S. H. Jung, J. H.
Lee, M. Yamada, R. Sethy, T.
Kawai, J. H. Jung*
*
external mechanical stimulus.
Page No. – Page No.
Finely Controlled Circularly
Polarized Luminescence of a
Mechano-Responsive
Supramolecular Polymer
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