Article
pubs.acs.org/Langmuir
Thermally Sensitive Self-Assembly of Glucose-Functionalized
Tetrachloro-Perylene Bisimides: From Twisted Ribbons to
Microplates
Kai Sun, Chengyi Xiao, Chunming Liu, Wenxin Fu, Zhaohui Wang,* and Zhibo Li*
Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190,
P. R. China
S Supporting Information
*
ABSTRACT: Chiral supramolecular structures are becoming
increasingly attractive for their specific molecular arrangements,
exceptional properties, and promising applications in chiral sensing
and separation. However, constructing responsive chiral supramolecular structures remains a great challenge. Here, glucosefunctionalized tetrachloro-perylene bisimides (GTPBIs) with thermally sensitive self-assembly behaviors are designed and synthesized.
In a methanol/water mixture, GTPBIs self-assembled into twisted
ribbons and microplates at 4 and 25 °C, respectively. Furthermore,
the ribbon structure was metastable and could transform into
microplates when the temperature was increased from 4 to 25 °C. Transmission electron microscopy (TEM) was used to track
the evolution of morphology and study the assembly mechanisms of correponding nanostructures at different time intervals. The
supramolecular structures were characterized with various techniques, including circular dichroism, TEM, scanning electron
microscopy, atomic force microscopy, ultraviolet−visible absorption, and fluorescence spectra. This study provides insight into
controlling molecular parameters and assembly conditions to construct chiral supramolecular structures.
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gas,28 switchable interfaces,9 and carbohydrate−lectin interactions.29,30 Herein, we report a thermally sensitive selfassembly of glucose-functionalized tetrachloro-perylene bisimdes (GTPBIs). Temperature has a significant effect on the
assembled structures. GTPBI assembled into twisted ribbons
and microplates in a methanol/water mixture at 4 and 25 °C,
respectively. The ribbon structure was metastable and could be
transformed into microplates when the temperature was
increased from 4 to 25 °C. In particular, we carefully explored
the time-dependent assembly processes and mechanisms of
these two supramolecular structures using transmission electron
microscopy (TEM) at different time intervals during the selfassembly process together with circular dichroism (CD)
spectra. The devices based on microplates revealed that
molecular arrangements were quite important for charge
transport performance.
INTRODUCTION
Self-assembly offers a versatile stratergy for creating wellorganized structures.1−3 In general, researchers could take
advantage of multiple intermolecular interactions and experimental conditions to tune and optimize the assembled
nanostructures.4−11 Perylene bisimides (PBIs) are promising
building blocks for n-type functional supramolecular architectures.12−14 The self-assembly of PBIs has been extensively
studied as the assembled supramolecular structures exhibit
unique properties and have promising applications in electronic
and optoelectronic nanodevices, such as organic field effect
transistors (OFETs) and organic photovoltaics (OPVs).15−17
Chirality is a universal phenomenon in biological systems
and is associated with numerous bioactivities. On one hand,
chiral molecules can assemble into chiral supramolecular
structures;18,19 on the other hand, chiral supramolecular
structures can be formed via chiral species-induced selfassembly of achiral molecules.20−24 Because of specific
molecular arrangements, many chiral supramolecular structures
possess exceptional properties and have potential applications
in chiral sensing and separation.25−27 Therefore, it is an urgent
challenge to construct chiral supramolecular structures with
unique quality via controlled self-assembly.18
Saccharides make up an important class of naturally available
chiral molecules that can induce chiral assembly because of
their inherent chiral centers and hydrogen bonding. Recently,
carbohydrate-based perylene bisimides have attracted considerable research interest because of their potentials in sensing of
© 2014 American Chemical Society
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EXPERIMENTAL SECTION
Materials and Methods. 1H nuclear magnetic resonance (NMR)
and 13C NMR spectra were recorded in deuterated solvents on a
Bruker AVANCE 400NMR spectrometer. 1H NMR chemical shifts are
reported in parts per million downfield from a tetramethylsilane
(TMS) reference using the residual protonated solvent as an internal
standard. Mass spectra (matrix-assisted laser desorption ionization
Received: June 27, 2014
Revised: August 27, 2014
Published: August 28, 2014
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Scheme 1. Chemical Structure of GTPBI
Figure 1. UV−vis absorption spectra of GTPBI in a methanol/water mixture (a) with the water content varied from 0 to 80 vol % at room
temperature (C = 0.05 mg/mL) and (b) at different temperatures in a 0.05 mg/mL methanol/water mixture [50/50 (v/v)].
time of flight) were determined on a Bruker BIFLEX III mass
spectrometer. Ultraviolet−visible (UV−vis) absorption spectra were
measured with a TU-1901 spectrophotometer in a 1 cm quartz cell.
Fluorescence spectra were recorded on a Hitachi F-4500 spectrofluorometer. CD spectra were recorded on a JASCO J-815
spectrometer. Specific rotation was obtained on a PerkinElmer
model 343 polarimeter. Dynamic light scattering (DLS) was
performed with a Malvern Zetasizer Nano ZS instrument. X-ray
diffraction (XRD) analysis was performed on a Rigaku D/MAX 2500
diffractometer. TEM images were obtained using a JEM-2200FS
instrument. Selected area electron diffraction (SAED) images were
obtained with a JEM-2100FS instrument. Scanning electron
microscopy (SEM) was performed with a JEOL-6700 field-emission
scanning electron microscope. Atomic force microscopy (AFM) was
performed in tapping mode (Nanoscope IIIa, Digital Instruments,
Inc.). The devices based on microplates formed from GTPBI were
fabricated on a Micromanipulator 6150 probe station through an
organic ribbon mask technique.
All chemicals were purchased from commercial suppliers and used
without further purification unless otherwise specified.
Synthesis of GTPBI. The synthetic route and characterization of
compounds are shown in the Supporting Information.
behaviors of GTPBI, UV−vis absorption and fluorescence
spectra were recorded for various methanol/water volume
ratios and concentrations (Figure 1 and Figures S2 and S3 of
the Supporting Information). When water was gradually added
into the GTPBI/methanol solution, the absorption spectra
displayed a bathochromic shift and the intensity decreased. Also
note that as the water content increased, the A0→0/A0→1 ratio
(Frank Condon principle) decreased, which was an indication
of PBI aggregation.31 In addition, a noticeable signal appeared
at longer wavelengths with an increase in water content. All
these characteristics suggested that the GTPBI molecules
underwent self-assembly. The corresponding fluorescence
spectra showed similar self-assembly characteristic in good
aggrement with UV−vis absorption spectra. As the water
content increased, the fluorescence intensity decreased
dramatically because of the quenching of aggregation.
Next, we used TEM to observe the aggregation nanostructure and morphology transition. Figure S4 of the Supporting
Information shows the coexistence of twisted fibers and
microplates. Considering the effects of hydrogen bonding
originating from hydroxyl groups of glucose,32−34 we assumed
that temperature might have a significant influence on the
resultant morphologies. The self-assembly of GTPBI was
performed at different temperatures. Systemic TEM measurements found that GTPBI formed twisted ribbons, microplates,
and irregular spheres at 4, 25, and 50 °C, respectively (Figure
2). In particular, left-handed twisted ribbons are clearly
observed in panels a and b of Figure 2 and Figure S5 of the
Supporting Information, indicating that the chiral groups
played a crucial role in the formation of chiral nanostructures.
The width of twisted ribbons is approximately tens of
nanometers, and the length ranges from hundreds of
nanometers to several micrometers. The thickness of twisted
ribbons estimated from TEM is around 13 nm (Figure S5 of
the Supporting Information). SEM images of microplates are
shown in Figure S6 of the Supporting Information. The
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RESULTS AND DISCUSSION
Scheme 1 shows the chemical structure of GTPBI. Glucose was
successfully grafted to the perylene chromophore via click
chemistry (Scheme S1 of the Supporting Information). As a
result of tetrachlorine substitution at the bay regions, GTPBI
exhibits solubility in common polar organic solvents (e.g.,
methanol and ethanol) that is better than those of other
reported carbohydrate-based perylene bisimides.28
The self-assembly of GTPBI proceeded via the selective
solvent addition method by the addition of water to the
GTPBI/methanol solution. Upon addition of water, an obvious
change in color from orange to red was observed immediately.
Then, noticeable aggregates were observed within 2 h, and their
amount grew with time, which indicated a transformation from
solution to suspension. To understand the aggregation
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microplates are approximately several micrometers long and
wide. AFM characterization revealed that the thickness of
microplates was approximately tens of nanometers (Figure S7
of the Supporting Information). It is worth noting that both
twisted ribbons and microplates were stable at 4 and 25 °C,
respectively. Both can maintain their morphology for at least 1
month at the specified temperature.
Considering the different morphologies at different temperatures, we investigated the absorption and fluorescence spectra
to study the aggregation behaviors at different temperatures.
From the absorption spectra (Figure 1b), the main absorption
peaks did not move with an increase in temperature from 4 to
50 °C, indicating that the three different supramolecular
structures had similar exciton coupling and intimate relations.35,36 In addition, the irregular spheres were least ordered
while the microplates were most highly ordered, which was
likely the reason for the observed nonmonotonous intensity
trends.
To gain a deep understanding of chirality, CD spectra were
recorded for the assembled structures at different temperatures.
Intense Cotton effects were observed for GTPBI in methanol/
water binary solvents at both 4 and 25 °C (Figure 3a). A
bisignate signal is indicative of chiral excitonic coupling that
arises when chromophores are aggregated in a helical fashion.37
The bisignate negative/positive signal with an increasing
wavelength (within the absorption limits of perylene
chromophores, from 375 to 575 nm) indicated a right-handed
or clockwise (P) helical arrangement of the transition dipoles of
Figure 2. TEM images of assemblies formed from GTPBI in a 0.1 mg/
mL methanol/water mixture [50/50 (v/v)] at (a) 4, (c) 25, and (d)
50 °C. (b) High-resolution TEM image of twisted ribbons [the white
arrows indicate the thickness of ribbons (see the Supporting
Information)].
Figure 3. CD spectra of GTPBI in a 0.1 mg/mL methanol/water mixture [50/50 (v/v)] at different temperatures: (a) annealed at 4, 25, and 50 °C
for 2 days, (b) assembled at 4 °C for 2 days followed by annealing at 25 and 50 °C for an additional 2 days, (c) assembled at 25 °C for 2 days
followed by annealing at 4 and 50 °C for an additional 2 days, and (d) assembled at 50 °C for 2 days followed by annealing at 4 and 25 °C.
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GTPBI molecules. Though microplates were apparently flat
and achiral, the intense CD signal suggested that these
microplates also had chiral molecular arrangements within the
assembled structures.
UV−vis absorption, fluorescence, and CD spectra clearly
reveal that twisted ribbons and microplates are closely
associated during the assembly process. To clarify this point,
we varied temperature to track the evolution of structure using
TEM. It was known that GTPBI assembled into microplates in
a methanol/water mixture. Using this as a pristine solution, we
did not observe a noticeable change in morphology when the
sample solution temperature changed from 25 to 4 °C and
from 25 to 50 °C. This suggested that preformed microplates
were quite stable versus a mild change in temperature
regardless of heating or cooling. In contrast, twisted ribbons
can be easily converted into microplates when the sample
solutions are heated from 4 to 25 °C or from 4 to 50 °C. From
TEM characterization, the ratio of microplates to ribbons
increased significantly with annealing time. Furthermore, if the
sample solution was first annealed at 50 °C for 2 days before
being cooled, a different final temperature resulted in the
formation of distinct nanostructures. For example, twisted
ribbons and microplates were obtained by cooling the solution
from 50 to 4 °C and from 50 to 25 °C, respectively (Figure 4).
into microplates. Notably, some small irregular aggregates
appeared when the twisted ribbon solution was heated from 4
to 50 °C. Therefore, the signal of the CD spectrum at 50 °C
was less intense than that at 25 °C. The CD spectra in Figure
3b were in line with the changes in morphology. Moreover,
twisted ribbons and microplates were obtained when the
sample solution temperature was reduced from 50 to 4 °C and
from 50 to 25 °C, respectively, which agreed well with the CD
signal from silent to active shown in Figure 3d. Specifically, CD
signals also appeared at longer wavelength, which could be
assigned to chiral scattering of the light as a result of the
interaction of the light with the chiral nanostructures.27
Given the results discussed above, we believed the twisted
ribbons formed at 4 °C were at an upper state in comparison
with the microplates formed at 25 °C. When the temperature
was increased, the arranged molecules in the ribbons would
absorb energy to clear the potential barrier to reach a lowerenergy state, accompanied by molecular rearrangements to
form microplates.
The crystalline structure of microplates was investigated by
XRD. The XRD patterns (Figure S10 of the Supporting
Information) displayed a series of diffraction peaks with 2θ =
5.0°, 10.0°, and 19.9°, implying the formation of a well-ordered
crystalline structure. The d value corresponding to 2θ (5.0°) is
1.76 nm, which is in agreement with the molecular length. The
SAED pattern of microplates in Figure S11 of the Supporting
Information confirmed ordered arrangements within the
crystals.
To gain a better understanding of the formation mechanism,
we traced the evolution of morphologies with TEM at different
time intervals (Figure 5 and Figure S12 of the Supporting
Information). The proposed mechanism is illustrated in
Scheme 2. In the initial stage, irregular spheres formed when
water was added to the GTPBI/methanol solution because of
the sudden change in solubility. Then through synergistic
effects of π−π stacking, hydrogen bonding, and solvent−solute
interactions, the preformed spheres aggregated and fused into
rough rods/ribbons. Gradually, twisted ribbons and microplates
formed at 4 and 25 °C, respectively, after a long period of
progression.
For organic semiconductor materials, we have performed
standard current−voltage (I−V) measurements of microplates
formed from GTPBI at 25 °C using the so-called organic
ribbon mask technique (Figure S13 of the Supporting
Information). The conductivity of microplates was relatively
lower compared to values published in other reports. We
thought it was caused by the twisted molecular arrangements as
shown in Scheme 2, which was disadvantageous for the charge
carrier to transport along the π−π stacking direction.
Figure 4. TEM images of assemblies formed from GTPBI in a 0.1 mg/
mL methanol/water mixture [50/50 (v/v)] at different temperatures:
(a) assembled at 4 °C for 2 days followed by annealing at 25 °C for an
additional 2 days, (b) assembled at 4 °C for 2 days followed by
annealing at 50 °C for an additional 2 days, (c) assembled at 50 °C for
2 days followed by annealing at 4 °C for an additional 2 days, and (d)
assembled at 50 °C for 2 days followed by annealing at 25 °C for an
additional 2 days.
■
CONCLUSIONS
In summary, we have successfully constructed chiral supramolecular structures via the thermally sensitive self-assembly of
GTPBI, which forms twisted ribbons and microplates at
different temperatures. We investigated the corresponding
transformation of morphology with the change in temperature
and demonstrated that temperature can affect the interaction of
glucose moieties, which ultimately determined the assembly
nanostructures in solution. This research provides insight into
controlling molecular parameters and assembly conditions to
create chiral supramolecular structures.
CD spectra clearly reveal the change in chirality when the
temperature is varied (Figure 3). As microplates formed at 25
°C were stable, the CD spectra (Figure 3c) almost remained
the same when the temperature changed, which was consistent
with the TEM and SEM results. However, compared to
microplates, the twisted ribbons formed at 4 °C were
metastable with an increase in temperature and transformed
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Figure 5. TEM images of the evolution of microplates formed from GTPBI in a 0.1 mg/mL methanol/water mixture (water content of 50 vol %) at
25 °C at different time intervals: (a) 0 min, (b) 5 min, (c) 15 min, (d) 30 min, (e) 45 min, (f) 60 min, (g) 2 h, (h) 6 h, (i) 8 h, (j) 10 h, (k) 12 h, and
(l) 24 h.
Notes
Scheme 2. Illustration of the Self-Assembly Mechanism for
Twisted Ribbons and Microplates of GTPBI
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (21225209, 51225306, and 91027043).
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ASSOCIATED CONTENT
S Supporting Information
*
Details of synthesis, specific rotations, optical spectra, additional
microscopy images, XRD patterns, and DLS spectra. This
material is available free of charge via the Internet at http://
pubs.acs.org.
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AUTHOR INFORMATION
Corresponding Authors
*E-mail: [email protected].
*E-mail: [email protected].
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