Solid-State Light Emission Controlled by Tuning the Hierarchical Superstructure of Self-Assembled Luminogens

Article abstract of DOI:10.1002/adfm.201707075

Solid-state luminescence is an important strategy for color generation via molecular self-assembly. Here, a new luminogen (AT₃EMIS) containing both a rigid chromophore and a flexible dendron is designed and synthesized for multicolor emission.

Full text of DOI:10.1002/adfm.201707075

FULL PAPER
Luminogens
www.afm-journal.de
Solid-State Light Emission Controlled by Tuning the
Hierarchical Superstructure of Self-Assembled Luminogens
Dae-Yoon Kim, Jahyeon Koo, Seok-In Lim, and Kwang-Un Jeong*
structure and the molecular packing
structure. Even a slight chemical modi-
Solid-state luminescence is an important strategy for color generation via
[7]
molecular self-assembly. Here, a new luminogen (AT EMIS) containing both
fication can have a significant effect on
the molecular packing structure and can
cause unpredictable properties in the
3
a rigid chromophore and a flexible dendron is designed and synthesized for
multicolor emission. The emission energy of the target material is precisely
controlled by adjusting three different columnar arrays through thermal and
mechanical stimulation. With well-defined supramolecular organizations in
different length scales, the luminescent properties of the light switch can be
tuned.
[
8]
emitted light. Therefore, to experimen-
tally and theoretically study the molecular
self-assembly, the rational and delicate
design, and synthesis of new lumino-
[
9]
gens must precede. Liquid crystal (LC)
phase showing the orientational order
and the translational motion observed
in supramolecular luminogens can provide many opportuni-
ties to understand the relationship between molecular struc-
ture, packing symmetry, and luminescent property in different
1
. Introduction
Luminescence is one of the most useful processes for gener-
ating colors from nature to increase species awareness, to attract
food, and to defend the attacker.[ The luciferase of beetle is a
good example of biological materials, which emits a wide range
of luminescent colors from green to red depending on the sen-
sitivity to factors as denaturing conditions.[ Inspired by nature,
material scientists and engineers have tried to develop lumi-
nescent materials by utilizing conjugated polymers, inorganic
nanoparticles, and alloyed nanobelts.[ Among them, organic
chromophores are often better suited for practical applications
[
10]
length scales. In addition, owing to the dynamic nature of
LC molecules, luminogens that reveal the mesomorphic transi-
tion behaviors can induce color changes by applying external
1]
[
11]
forces. Here, we report a novel supramolecular luminogen
that exhibits multicolor luminescence which can be switched
ON and OFF by thermal and mechanical stimulation.
2]
3]
2
. Results and Discussions
[
4]
in sensors and displays due to the good processability. How-
ever, conventional luminophores such as thiophene, naphtha-
lene, and pyrene derivatives loss their photophysical properties
in the bulk state. They only produce luminescence in a dilute
state.[ In the recent years, there has been a growing demand
for the development of luminescent materials that can con-
vert chemical energy into light energy in the solid state. For
example, thin films made from luminogens in the real world
are widely used in organic light emitting devices.[ Therefore,
the development of a luminogen that emits brighter emission
by forming an ordered structure in the solid state through a
self-assembly process is critical to the next generation of smart
material research.
2.1. Photophysical Properties and Phase Behaviors
of Programmed Luminogens
5]
The target material was newly designed and synthesized
starting from a cyano-substituted divinylene arene deriva-
tive (Figure 1a). The Knoevenagel reaction of the aldehyde
[
12]
derivative and the acetonitrile moiety yielded a luminogen.
6]
AT EMIS was obtained by Steglich esterification with 3,4,5-tris-
3
dodecyloxybenzoic acid. Synthetic methods and purification
procedures are described in Figures S1–S6 in the Supporting
Information. The chemical structure and purity of AT EMIS,
3
and its intermediates are confirmed by 1H and C nuclear
magnetic resonance (NMR) spectra, and matrix assisted laser
desorption and ionization time-of-flight (MALDI-ToF) anal-
13
Since the photophysical properties of a material are the
result of molecular assemblies that can be influenced by the
interaction of subtle factors, it is very difficult to define solid-
state luminescence without taking into account the chemical
ysis. AT EMIS is a rigid chromophore-based compound, but
3
it exhibits high solubility in common organic solvents such
as chloroform, hexane, and toluene due to the asymmetrically
attached dendron.
Dr. D.-Y. Kim, J. Koo, S.-I. Lim, Prof. K.-U. Jeong
Department of Polymer-Nano Science and Technology
Chonbuk National University
Jeonju 54896, Korea
E-mail: kujeong@jbnu.ac.kr
Strong solid-state luminescence can be found in AT EMIS
3
because of the aggregation induced emission (AIE) characteris-
[
13]
tics. The UV–vis absorption spectra of AT EMIS are recorded
3
in tetrahydrofuran (THF) solutions (Figure S7, Supporting
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.201707075.
Information). AT EMIS shows two absorption bands at around
3
3
20 and 370 nm, corresponding to the benzoate function and
[
14]
DOI: 10.1002/adfm.201707075
the luminogen moiety, respectively. When the 370 nm UV
Adv. Funct. Mater. 2018, 1707075
1707075 (1 of 8)
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.advancedsciencenews.com
www.afm-journal.de
Figure 1. Molecular structure a), luminescence property b), and thermal behaviors c) of AT EMIS.
3
light with 1.5 mW cm−2 intensity is irradiated for exciting the
sample, it does not show any emission in the entire visible
2.2. Structure Identification of Columnar Superstructure
region. The AT EMIS has a drastic change in emission inten-
To gain deeper insight into the self-assembled supramolecular
organization, we carefully examined the molecular packing
3
sity from a nonluminescent solution (SOL) state to a strong
luminescent suspension (SUS) state as demonstrated in the
Figure 1b. It is widely accepted that the rotational motion of
luminogen annihilates the excited state. Note that the cyano-
substituted divinylene arene derivative has a twisted molecular
geometry due to the steric factor of the cyanide unit, which
structure of AT EMIS in three ordered states using wide-angle
3
X-ray diffraction (WAXD). A macroscopically aligned sample
is prepared by the mechanically extruding the AT EMIS com-
3
pound at 155 °C and then quenched to 25 °C. The uniaxially
oriented sample is thermally annealed at 105 °C before the 2D
WAXD measurement. The direction of the incident X-ray beam
is always normal to the extrusion direction (ED). As shown
[15]
allows a nonradiative process. Addition of a copious amount
of methanol (MeOH) as a poor solvent into the SOL state of
AT EMIS in THF leads the molecular aggregation. Recognition
in Figure 2a, the 2D WAXD pattern of AT EMIS at 155 °C is
3
3
of chemical building blocks through intermolecular interac-
tions can create physical constraints and limit intramolecular
obtained with high quality. The diffused ring pattern in the
wide-angle region (d = 0.48 nm) indicates that alkyl chains are
rotations.[ When the radiation channel is opened, AT EMIS
16]
in the melt state. In the small-angle region, the reflection at
[18]
3
emits light. The luminescence quantum yields in the SOL and
SUS states are 0.01 and 0.17, respectively, thus demonstrating
d = 4.52 nm is obviously divided into six spots at an azimuthal
angle of 60° (Figure S9, Supporting Information). Due to the
the concomitant AIE effect of AT EMIS.
lack of higher order diffractions, the ordered phase of AT EMIS
3
3
[
19]
To understand the intense light emission of AT EMIS in bulk
at 155 °C can be considered as a low-ordered LC mesophase.
3
state, we tried to figure out how the molecules self-assembled
The vertices of the hexagon corresponding to the (100) reflec-
into an ordered structure. Phase transformation of AT EMIS is
tion indicate that AT EMIS forms the columnar hexagonal
3
3
first identified using differential scanning calorimetry (DSC).
The transition temperatures and associated enthalpy values are
(Col ) organization with a long-range positional order between
H
[
20]
the self-assembled columns.
Since the AT EMIS lumi-
3
shown in Figure 1c. The DSC thermogram of AT EMIS shows
nogen is not disc shaped, it can be deduced that the disc in the
column is composed of more than one molecule. The number
(n) of molecules constituting a single disc of a column can be
3
three endothermic peaks during the heating process. The DSC
thermogram obtained in the subsequent cooling process is
consistent with that attained in the heating process, indicating
enantiotropic thermal behaviors.[ This compound exhibits
a good thermal stability up to 375 °C (Figure S8, Supporting
Information).
−
1
calculated by the following equation, n = VρN M , where NA,
A
W
17]
M , V, and ρ is Avogadro number, molecular weight, volume,
W
and density of the unit cell, respectively. Assuming a typical ρ
−
3
of LC material is about 1.0 g cm , the unit cell with a thickness
Adv. Funct. Mater. 2018, 1707075
1707075 (2 of 8)
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.advancedsciencenews.com
www.afm-journal.de
Figure 2. 2D WAXD of uniaxially oriented AT EMIS at 155 °C a) and 25 °C c). Schematic illustration of molecular packing model for ColH b) and Col d).
3
R
of 0.45 nm contains six molecules.[21] The discs consisting of
In this circumstance, we focus to figure out the detail molec-
ular packing structure of AT EMIS in the K phase. Since the
AT EMIS hexamers are stacked flat with each other without
3
3
1
[22]
strong π–π stacking.
Therefore, the long axis of disc is
diffraction pattern of the oriented sample matches well with
the powder sample, it can be determined that the diffraction at
d = 0.45 nm is observed at 58° out of the ED (Figure 2c). These
two pairs of peaks explain that the hexamer discotic building
block is tilted 58° with respect to the ab-plane. Note that
aligned along the ED. Note that the rotational isotropy formed
by the disordered state of alkyl chains creates the circular col-
umns.[ Here, the orientation direction of the column axis
23]
(CA) is normal to the ED, and the lattice parameter of ColH
structure is a = b = 5.21 nm and γ = 60° (Figure 2b).
At 105 °C, many sharp diffraction patterns are appeared in both
small- and wide-angle regions (Figure S10, Supporting Informa-
AT EMIS forms a conventional head-to-head dimer by the
3
[26]
intermolecular hydrogen bond between two hydroxyl groups.
The local dipole moments of the cyanide unit then induce the
side-to-side intermolecular coupling of the dimeric building
tion). This means that a highly ordered crystal (K ) phase appears,
2
[27]
forming the intracolumnar disc stacking interactions. Upon
decreasing the temperature to 25 °C, diffraction peaks in the wide-
angle region are getting narrow and shifting to higher 2θ-angles,
blocks and construct the disc-like arrangement.
However,
the series of diffraction arc at 2θ = 5.25°, 10.5°, and 15.7° is
observed on the meridian, which can be assigned as the (001),
(002), and (003), respectively. This result supports that three
hexameric discs participating in a single column are rotated 90°
to the adjacent (ABA stacking) to minimize steric hindrances.
The slanted stacking of the hexameric disc in the next stratum
of the column is rotated around the CA. Careful structural
analysis gives an orthorhombic unit cell with dimensions of
a = 5.35 nm, b = 5.52 nm, c = 1.68 nm, and α = β = γ = 90° via the
[24]
indicating the formation of true crystal (K ) phase. Since the
1
structural change of the crystal-to-crystal phase transition requires
a tremendous amount of energy, the molecular packing structure
[25]
in the K phase should resemble the K phase. As shown in
2
1
Figure S11 in the Supporting Information, it is realized that the
tendency of the diffraction pattern of the uniaxially oriented K1
sample is not significantly different from that of the K sample.
2
Adv. Funct. Mater. 2018, 1707075
1707075 (3 of 8)
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.advancedsciencenews.com
www.afm-journal.de
refinement of the reciprocal lattice, and this phase is close to a
chromophore, while the wide-angle halo (d = 0.47 nm) repre-
sents the average distance between the flexible dendrons. At
columnar rectangular (Col ) structure as illustrated in Figure 2d.
R
1
55 °C, a typical pseudo focal conic texture of LC mesophase
[
29]
is observed. The K phase at 105 °C shows the defect aggre-
2
2
.3. Tunable Luminescence of Light for Multicolor Switch
gates across the pseudo focal conic texture. Significant enhance-
ments in birefringence during the K -to-K phase transition are
2
1
Based on the structure identification, the molecular packing
due to the close molecular packing of the luminogen cores and
the crystallization of aliphatic tails.
[
30]
structures of AT EMIS can be manipulated by varying the tem-
3
perature. As shown in Figure 3a, the overall phase transition
We have found that a simple thermal treatment on the
behaviors are summarized in polarized optical microscopy
AT EMIS compound triggers a change in the luminescence
3
(
POM) images of AT EMIS. As expected, the Iso state of
color. Interestingly, AT EMIS in the optical cell exhibits the
3
3
AT EMIS is confirmed at 185 °C by a complete dark state.
remarkable thermochromic luminescent behaviors in the solid
3
The WAXD of AT EMIS in the Iso state exhibits only amor-
state. Figure 3b shows the luminescence changes of AT EMIS
3
3
[28]
phous halos at 2θ = 2.43° and 2θ = 18.8°. The low-angle halo
d = 3.64 nm) indicates the average periodicity of electron
density fluctuations between the nanophase separated rigid
measured at different phases during the cooling process from
185 to 25 °C. The thermochromic luminescence behaviors are
detected between green and blue, which is easily distinguished
(
Figure 3. POM images of AT EMIS at different temperatures a). Macroscopic images of AT EMIS during cooling process under 370 nm UV light
3
3
irradiation b). Luminescence spectra of AT EMIS at each phase c), and the maximum intensity shift behaviors with respect to temperature (inset).
3
Adv. Funct. Mater. 2018, 1707075
1707075 (4 of 8)
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.advancedsciencenews.com
www.afm-journal.de
by the naked eye.[31] The photophysical properties of small mole-
cules with π-electronic conjugation systems depend not only
on the individual chemical functions but also on the intermo-
lecular physical bonds, so that it is possible to manipulate the
bathochromic shift compared to the LC mesophase. The red-
shift of the emission spectrum for the K phase is the result of
2
increased interactions of the disc and generates the electronic
[
36]
delocalization through the π-conjugation system.
Finally,
solid-state luminescence of AT EMIS through appropriate heat
the K phase is converted to the K phase at room tempera-
3
2
1
treatment.[ In addition, the spectral features of absorbance
properties are somewhat different from each phase (Figure S12,
Supporting Information). These observations further support
that the arrangements of the luminogens in the three ordered
structures are changed.[
32]
ture, and the luminescence intensity is remarkably enhanced
at λmax = 530 nm. The redshift in the emission spectrum for the
transition from the K phase to the K phase can be explained by
2
1
the increased interchromophoric interaction, which is evident
by another redshift for the transition from the LC mesophase
33]
[
37]
At 185 °C, the solid-state of AT EMIS does not emit any dis-
to the K2 phase.
The additional increase in luminescence
3
cernible light because the long-range molecular order is totally
disappeared and the intramolecular rotation in the Iso state is
intensity should be originated from the complete restriction
of AT EMIS rotational motion, together with the closer packing
3
activated.[ When AT EMIS molecules enter the LC mesophase,
34]
of the disc in the self-assembled column.
[38]
3
they emit brilliantly. A broad emission peak with λmax = 490 nm
is detected, as shown in Figure 3c. Considering the molecular
packing structure in the LC mesophase, we have found that the
restriction of intramolecular motion is useful for preventing
nonradiative relaxation. In the LC mesophase, the intramolec-
Obtaining the photoluminescence property of new mate-
rials at room temperature is very important for practical appli-
cation of optical devices because it is advantageous for low
[
39]
cost process and high efficiency production.
When gently
grinding AT EMIS with pestle at room temperature, the green
3
ular rotational motion of AT EMIS is reduced by concomitantly
emission by irradiation of 370 nm light instantly changes to
intense yellow emission. Figure 4a shows the mechanochromic
luminescence behaviors. When the yellow powder of crushed
3
[35]
increasing planarity through dimer formation.
When the temperature is lowered to 105 °C, AT EMIS in
3
the K phase emits light at λ
= 520 nm, which is a 30 nm
AT EMIS is fumed directly by dichloromethane, it is completely
2
max
3
Figure 4. Macroscopic photographs a), luminescence spectra b), and diffraction patterns c) of AT EMIS at the pristine powder solid, after the mechan-
3
ical grinding state, and the subsequent dichloromethane fuming process.
Adv. Funct. Mater. 2018, 1707075
1707075 (5 of 8)
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.advancedsciencenews.com
www.afm-journal.de
Figure 5. Procedures for switching the multicolor luminescence via the thermochromic and mechanochromic behaviors of AT EMIS.
3
restored to green as the original AT EMIS. It is evident that
return from Col to Col due to partial melting and subsequent
S R
3
the AT EMIS powder is divided into two areas: yellow (external
recrystallization.
3
ring) and green (center ring). The emission spectra of the ini-
tial, ground, and fumed states are summarized in Figure 4b.
To find an answer for the main driving force of the mecha-
nochromic luminescence behaviors, the 1D WAXD patterns are
obtained after applying the mechanical force. Figure 4c shows
a dramatic reduction in peak intensity with increased peak
width for the ground sample. This means that the intermo-
If the emission of AT EMIS can be controlled by heat as well
3
as mechanical forces, AT EMIS allows us to design a smarter
3
emissive memory system. As shown in Figure 5, the distinctive
yellow, green, and blue emissions from the letter “SCI” can be
clearly observed in Col , Col , and Col , respectively. The ground
S
R
H
AT EMIS showing yellow color placed on the glass substrate
3
yields the initial state (i). Upon exposure to dichloromethane
vapor at room temperature, the ColS film is converted to the
ColR film (ii) and turns green. When the ColR film is subse-
quently placed on a hot stage and heated to form the ColH phase
lecular interaction of AT EMIS in the ground state is weaker
3
than initial state.[ However, 1D WAXD pattern of the ground
40]
sample still shows a reflection peak at the low-angle region of
2
θ = 2.26°, suggesting the formation of a shear-induced
(iii), AT EMIS becomes blue. When the film reaches to the Iso
3
columnar phase (Col ). The mechanical shear applied to
AT EMIS reorganizes the molecular arrangement from Col to
Col with the intercolumnar distance of d = 3.94 nm. It is worth
mentioning the fact that this kind of grinding process is hard
state (iv), we cannot find the any emission of light. The multi-
color switching protocol is fully reversible, so we can easily turn
ON and OFF the luminescence and even adjust the color. For
instance, if the luminogen shows a dark color (iv) at 185 °C, the
substrate is quenched to 25 °C to generate a green emission
(ii). Then we can obtain the yellow emission (i) by shearing the
S
3
R
S
to lead a perfect conversion of the AT EMIS packing symmetry
3
because the mechanical force is unevenly applied to the pristine
powder in the bulk state.[ The residual diffraction peaks cor-
41]
AT EMIS film on the glass substrate with a stick. Increasing the
3
responding to the Col domain are included in the 1D WAXD
pattern obtained in the ground sample.
temperature directly to 155 °C will emit blue (iii) as expected.
R
The formation of Col results in a bathochromic shift and a
S
broad emission spectra at λmax = 590 nm.[ The slippage of the
molecular stack by mechanical shear creates a larger π-electron
conjugation system.[ The partially overlapped luminogens
are arranged more linearly. On the other hand, luminogens
aligned with the ABA fashion in ColR show a small portion
of the overlap as noted above, so they display emission bands
at shorter wavelengths (λmax = 530 nm). The reversibility of
mechanochromic luminescence is further investigated. When
fumed with dichloromethane, the emission color and diffrac-
tion peak are fully recovered to their initial state, indicating the
42]
3
. Conclusion
43]
We introduced a new luminogen (AT EMIS) that can switch the
3
luminescent color by applying thermal as well as mechanical
stimulation. Our experimental results indicated that under-
standing the self-assembled hierarchical superstructures is one
of the easiest and most important ways to predict and adjust the
emission energy of the target material. By precisely controlling
three different columnar structures (Col , Col , and Col ) of
R
H
S
AT EMIS, the solid-state luminescence can be reversibly switched
3
Adv. Funct. Mater. 2018, 1707075
1707075 (6 of 8)
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.advancedsciencenews.com
www.afm-journal.de
from green to blue, and yellow. Due to straightforward synthesis
Acknowledgements
and precise structure manipulation, AT EMIS can be a good
3
This work was mainly supported by the Mid-Career Researcher Program
2016R1A2B2011041), MOTIE-KDRC (10051334), and BRL (2015042417)
candidate for next generation luminescent materials that can be
applied to memory devices, security inks, and medical diagnoses.
(
of Korea.
4
. Experimental Section
Conflict of Interest
Materials and Characterization: All reagents were commercially obtained
and used without further purification. Column chromatography was
performed using the silica gel 60 (Merck). NMR spectra were recorded
on a spectrometer (Varian Oxford As500). MALDI-ToF mass (Voyager-DE
STR Workstation) experiment was conducted to identify the chemical
structure and purity. The thermal behaviors were monitored by using
the DSC (Perkin Elmer PYRIS) and POM (Nikon Eclipse). The WAXD
The authors declare no conflict of interest.
Keywords
chromophores, liquid crystals, luminescence, phase transitions,
supramolecular chemistry
measurements were used by CuK X-ray (Rigaku). Thermal stability
α
was determined by thermogravimetric analysis (TGA) (TA Q50). The
molecular simulation program (Accelrys Cerius) was utilized to calculate
the energy minimized geometry. Absorption spectra were detected by a
spectrophotometer (Scinco S3100). Emission spectra were taken by a
spectrofluorometer (Shimadzu RF6000).
Received: December 6, 2017
Revised: January 4, 2018
Published online:
Synthesis of Cyano-Substituted Divinylene Arene: 4-Hydroxybenzaldehyde
(16.4 mmol) and 1,4-phenylenediacetonitrile (6.6 mmol) were dissolved
in 1-propanol (18 mL) and acetic acid (0.79 mL). The solution was
heated at reflux under nitrogen atmosphere and piperidine (0.97 mL)
was carefully added. After 24 h the reaction mixture was cooled to room
[
1] a) R. J. D. Tilley, Colour and the Optical Properties of Materials, Wiley-
VCH, Weinheim 2010; b) D.-Y. Kim, C. Nah, S.-W. Kang, S. H. Lee,
K. M. Lee, T. J. White, K.-U. Jeong, ACS Nano 2016, 10, 9570.
2] a) V. R. Viviani, D. T. Amaral, D. R. Neves, A. Simões,
F. G. C. Arnoldi, Biochemistry 2013, 52, 19; b) K. V. Wood, Y. A. Lam,
W. D. McElroy, Luminescence 1989, 4, 289.
temperature, and the yellow solid was filtered, and washed with methanol
1
(
yield: 83%). H NMR (400 MHz, dimethyl sulfoxide (DMSO)-d):
[
δ = 8.01 (s, 2H), 7.85 (m, 4H), 7.76 (m, 4H), 6.95 (m, 4H) ppm.
Synthesis of 3,4,5-Trisdodecyloxybenzoic Acid: 1-Bromododecane
(
217.0 mmol) was slowly added, after K CO (330.0 mmol) was added
2 3
into the solution of methyl 3,4,5-trihydroxybenzoate (54.0 mmol) in
dried dimethylformamide (100 mL). The mixture was additionally
stirred for 12 h at 100 °C. The gummy solid obtained by filtration and
evaporation was dissolved in chloroform. The resulting mixture was
[3] a) X. Jia, J. Li, E. Wang, Small 2013, 9, 3873; b) L. Antolini,
E. Tedesco, G. Barbarella, L. Favaretto, G. Sotgiu, M. Zambianchi,
D. Casarini, G. Gigli, R. Cingolani, J. Am. Chem. Soc. 2000, 122,
9006.
washed with distilled water and dried over MgSO . The crude product
was recrystallized from acetone. The filtered and dried powder was
refluxed in the NaOH (30.0 mmol) solution with ethanol (100 mL) for
[4] a) S. Yagai, T. Seki, H. Aonuma, K. Kawaguchi, T. Karatsu,
T. Okura, A. Sakon, H. Uekusa, H. Ito, Chem. Mater. 2016, 28, 234;
b) D.-Y. Kim, S.-A. Lee, M. Park, Y.-J. Choi, W.-J. Yoon, J. S. Kim,
Y.-T. Yu, K.-U. Jeong, Adv. Funct. Mater. 2016, 26, 4242.
4
6
h. After cooling the mixture to room temperature, 1000 mL of distilled
water was added. The resulting mixture was acidified with HCl. The
precipitate was then filtered, washed with deionized water, and dried
[
5] H. Wang, E. Zhao, J. W. Y. Lam, B. Z. Tang, Mater. Today 2015, 18,
65.
3
1
under vacuum to give a white solid (yield: 94%). H NMR (400 MHz,
[
6] P. R. Christensen, J. K. Nagle, A. Bhatti, M. O. Wolf, J. Am. Chem.
Soc. 2013, 135, 8109.
CDCl ): δ = 7.24 (s, 2H), 3.96 (m, 6H), 1.81 (m, 6H), 1.46 (m, 6H),
3
1
.39 (m, 48H), 0.86 (m, 9H) ppm.
[
[
7] Q. Li, Z. Li, Adv. Sci. 2017, 4, 1600484.
8] B. Zhang, C.-H. Hsu, Z.-Q. Yu, S. Yang, E.-Q. Chen, Chem.
Commun. 2013, 49, 8872.
Synthesis of AT EMIS: A solution of cyano-substituted divinylene
3
arene (1.19 mmol) in dried dimethylformamide (50 mL) was added
to a solution of 3,4,5-trisdodecyloxybenzoic acid (0.29 mmol), N-(3-
dimethylaminopropyl)-N’-ethylcarbodiimide hydrochloride (1.48 mmol),
and 4-(dimethylamino)pyridine (1.48 mmol) in dried chloroform
[
9] K. Binnemans, J. Mater. Chem. 2009, 19, 448.
[
10] D.-Y. Kim, D.-G. Kang, M.-H. Lee, J.-S. Kim, C.-R. Lee, K.-U. Jeong,
Chem. Commun. 2016, 52, 12821.
11] Y. Li, Z. Ma, A. Li, W. Xu, Y. Wang, H. Jiang, K. Wang, Y. Zhao, X. Jia,
ACS Appl. Mater. Interfaces 2017, 9, 8910.
(20 mL). After stirring the mixture for 72 h at room temperature, the
[
product was extracted with chloroform and water. The combined
organic layer was dried over MgSO . The crude product was purified by
4
column chromatography with silica gel using ethyl acetate:methylene
chloride = 1:3 to yield a pale yellow powder (yield: 68%). H NMR
[12] F. Aparicio, S. Cherumukkil, A. Ajayaghosh, L. Sánchez, Langmuir
2016, 32, 284.
[13] Y. Sagara, K. Kubo, T. Nakamura, N. Tamaoki, C. Weder, Chem.
Mater. 2017, 29, 1273.
[14] a) M. Kim, D. R. Whang, J. Gierschner, S. Y. Park, J. Mater. Chem.
C 2015, 3, 231; b) D.-Y. Kim, S.-A. Lee, D. Jung, J. Koo, J. S. Kim,
Y.-T. Yu, C.-R. Lee, K.-U. Jeong, Soft Matter 2017, 13, 5759.
1
(
(
4
400 MHz, CDCl ): δ = 7.95 (d, 2H), 7.84 (d, 2H), 7.66 (m, 4H), 7.51
3
s, 1H), 7.49 (s, 1H), 7.43 (d, 2H), 7.32 (d, 2H), 6.89 (d, 2H), 5.67 (s, 1H),
1
3
.08 (m, 6H), 1.85 (m, 6H), 1.38 (m, 54H), 0.83 (t, 9H) ppm;
C
NMR (125 MHz, CDCl ): δ = 156.5, 158.2, 152.7, 143.8, 142.7, 141.4,
3
1
7
1
36.7, 135.4, 132.4, 131.3, 126.9, 122.8, 117.9, 116.2, 110.5, 109.5, 108.1,
3.8, 69.7, 31.9, 29.8, 25.7, 24.1, 13.5 ppm; MS (MALDI-ToF) m/z calcd:
[
15] Y. Q. Dong, J. W. Y. Lam, B. Z. Tang, J. Phys. Chem. Lett. 2015, 6, 3429.
16] Z. Ma, M. Teng, Z. Wang, S. Yang, X. Jia, Angew. Chem., Int. Ed.
013, 52, 12268.
+
021.46 [M+Na] ; found: 1043.96.
[
[
2
17] D.-Y. Kim, S. Shin, W.-J. Yoon, Y.-J. Choi, J.-K. Hwang, J.-S. Kim,
C.-R. Lee, T.-L. Choi, K.-U. Jeong, Adv. Funct. Mater. 2017, 27,
Supporting Information
1
606294.
Supporting Information is available from the Wiley Online Library or
from the author.
[18] M. Park, Y.-J. Choi, D.-Y. Kim, S.-H. Hwang, K.-U. Jeong, Cryst.
Growth Des. 2015, 15, 900.
Adv. Funct. Mater. 2018, 1707075
1707075 (7 of 8)
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.advancedsciencenews.com
www.afm-journal.de
[
[
[
[
[
[
[
19] M. E. Tousley, X. Feng, M. Elimelech, C. O. Osuji, ACS Appl. Mater.
Interfaces 2014, 6, 19710.
20] E. Westphal, M Prehm, I. H. Bechtold, C. Tschierske, H. Gallardo, J.
Mater. Chem. C 2013, 1, 8011.
[32] S. S. Babu, M. J. Hollamby, J. Aimi, H. Ozawa, A. Saeki, S. Seki,
K. Kobayashi, K. Hagiwara, M. Yoshizawa, H. Möhwald,
T. Nakanishi, Nat. Commun. 2013, 4, 1969.
[33] Y. Sagara, T. Kato, Angew. Chem., Int. Ed. 2011, 50, 9128.
[34] S.-J. Yoon, J. H. Kim, K. S. Kim, J. W. Chung, B. Heinrich,
F. Mathevet, P. Kim, B. Donnio, A.-J. Attias, D. Kim, S. Y. Park, Adv.
Funct. Mater. 2012, 22, 61.
[35] B. Huitorel, Q. Benito, A. Fargues, A. Garcia, T. Gacoin, J.-P. Boilot,
S. Perruchas, F. Camerel, Chem. Mater. 2016, 28, 8190.
[36] S. Yamane, Y. Sagara, T. Kato, Chem. Commun. 2013, 49, 3839.
[37] K. P. Gan, M. Yoshio, T. Kato, J. Mater. Chem. C 2016, 4, 5073.
[38] W. W. H. Wong, C.-Q. Ma, W. Pisula, A. Mavrinskiy, X. Feng,
H. Seyler, D. J. Jones, K. Müllen, P. Bäuerle, A. B. Holmes, Chem.
Eur. J. 2011, 17, 5549.
21] T. Shimogaki, S. Dei, K. Ohta, A. Matsumoto, J. Mater. Chem. 2011,
2
1, 10730.
22] X. Tan, L. Kong, H. Dai, X. Cheng, F. Liu, C. Tschierske, Chem. Eur.
J. 2013, 19, 16303.
23] D.-Y. Kim, D.-G. Kang, S. Shin, T.-L. Choi, K.-U. Jeong, Polym. Chem.
2
016, 7, 5304.
24] D.-Y. Kim, S.-A. Lee, Y.-J. Choi, S.-H. Hwang, S.-W. Kuo, C. Nah,
M.-H. Lee, K.-U. Jeong, Chem. Eur. J. 2014, 20, 5689.
25] D.-Y. Kim, S.-A. Lee, H. Kim, S. M. Kim, N. Kim, K.-U. Jeong, Chem.
Commun. 2015, 51, 11080.
[
[
[
26] M. Lehmann, S. Gloza, S. Roth, Chem. Mater. 2015, 27, 8181.
27] S. Varughese, J. Mater. Chem. C 2014, 2, 3499.
28] D.-Y. Kim, M. Park, S.-A. Lee, S. Kim, C.-H. Hsu, N. Kim, S.-W. Kuo,
T.-H. Yoon, K.-U. Jeong, Soft Matter 2015, 11, 58.
29] S. Herbst, B. Soberats, P. Leowanawat, M. Lehmann, F. Würthner,
Angew. Chem., Int. Ed. 2017, 56, 2162.
[39] X. Feng, R. Zhang, Y. Li, Y.-L. Hong, D. Guo, K. Lang, K.-Y. Wu,
M. Huang, J. Mao, C. Wesdemiotis, Y. Nishiyama, W. Zhang,
W. Zhang, T. Miyoshi, T. Li, S. Z. D. Cheng, ACS Cent. Sci. 2017, 3, 860.
[40] S. Roy, A. Hazra, A. Banyopadhyay, D. Raut, P. L. Madhuri, D. S.
S. Rao, U. Ramamurty, S. K. Pati, S. K. Prasad, T. K. Maji, J. Phys.
Chem. Lett. 2016, 7, 4086.
[41] S.-J. Yoon, J. W. Chung, J. Gierschner, K. S. Kim, M.-G. Choi, D. Kim,
S. Y. Park, J. Am. Chem. Soc. 2010, 132, 13675.
[42] T. Butler, W. A. Morris, J. Samonina-Kosicka, C. L. Fraser, ACS Appl.
Mater. Interfaces 2016, 8, 1242.
[
[
30] L. Qian, B. Tong, J. Shen, J. Shi, J. Zhi, Y. Dong, F. Yang, Y. Dong,
J. W. Y. Lam, B. Z. Tang, J. Phys. Chem.
098.
31] M.-J. Teng, X.-R. Jia, S. Yang, X.-F. Chen, Y. Wei, Adv. Mater. 2012,
4, 1255.
B 2009, 113,
9
[
2
[43] M. Teng, Z. Wang, Z. Ma, X. Chen, X. Jia, RSC Adv. 2014, 4, 20239.
Adv. Funct. Mater. 2018, 1707075
1707075 (8 of 8)
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim