Kinetically Trapped Supramolecular Assembly of Perylene Dianhydride Derivative in Methanol: Optical Spectra, Morphology, and Mechanisms

Article abstract of DOI:10.1002/chem.201604212

Supramolecular self-assembly has attracted increasing attention as a breakthrough methodology in the fields of nanoscience and nanotechnology. Herein, a perylene dianhydride derivative (TP-PDA) self-assembles into well-defined nanospheres through a nuclea

Full text of DOI:10.1002/chem.201604212

A Journal of
Accepted Article
Title: Kinetically trapped supramolecular assembly of perylene
dianhydride derivative in methanol: optical spectra, morphology
and mechanisms
Authors: Meizhen Yin, Baozhong Lü, Shusen You, Pengyu Li, Chen Li,
and Klaus Müllen
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To be cited as: Chem. Eur. J. 10.1002/chem.201604212
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Kinetically trapped supramolecular assembly of perylene
dianhydride derivative in methanol: optical spectra, morphology
and mechanisms
[
a]
[a]
[a]
[b]
[b]
[a]
Baozhong Lü , Shusen You , Pengyu Li , Chen Li , Klaus Müllen and Meizhen Yin
Abstract: Supramolecular self-assembly has attracted increasing
attention as breakthrough methodology in the fields of
nanoscience and nanotechnology. In this study, perylene
solvents and substitution type.[20-21] a similar process has rarely
been studied for perylene tetracarboxydianhydride (PDA). The
latter serves as an important precursor of PMIs and PBIs,[22-25]
but is also an important chromophore in its own right. Its poor
solubility and the lack of chemical functionalization ask for new
suitably functionalized PDAs which then hold promise for a
different assembly behavior.
a
a
dianhydride derivative (TP-PDA) self-assembles into well-defined
nanospheres through a nucleation-growth process. The mechanisms
of this process are explored by spectral analysis, dynamic light
scattering (DLS) and scanning electron microscopy (SEM). Both in-
situ DLS and in-situ SEM reveal that the sizes of aggregated
nanospheres increase with time until the formation of equilibrium H-
aggregates. It shows that TP-PDA undergoes a kinetically trapped
assembly with a rapid transformation into the thermodynamically
favoured form, and this process can be finely tuned by reduced
concentration and increased temperature. Weak intermolecular
forces such π–π stacking, hydrogen bonding and solvophobic
interactions play an important role in the formation of nanostructures.
The work inspires us to explore other kinetically trapped
supramolecular assemblies that might be easily ignored due to the
short trapping time of commonly used experimental timescales.
In this work, we report a perylene tetracarboxydianhydride
derivative bearing four phenyoxy groups in the bay-region (TP-
PDA) (Scheme 1).[
26,27]
This chromophore self-assembles into
well-defined nanospheres through an autocatalytic process in
polar protic solvent MeOH. The sizes of aggregated
nanospheres increased with time. The mechanisms of
supramolecular assembly were explored by optical spectra,
suggesting the existence of kinetically trapped products.
Introduction
Self-assembly provides an attractive way to control the
properties and performance of organic materials.[1-7] The
formation of complex nanostructures during self-assembly based
on the delicate balance between various weak intermolecular
forces have been studied as a function of the molecular building
blocks and the processing conditions.[ Recent studies have
8]
shown that the first step of the self-assembly pathway can
furnish kinetically trapped products.[
9-14]
These observations
inspired us to explore the growth of ordered nanostructures by
controlling the “trapping” process.
Perylene carboxyanhydride and -imide dyes display
exceptional chemical, thermal, and photochemical stability with
high fluorescence quantum yields in organic solvents.[15-18]
Further, these chromophore systems exhibit rich self-asssembly
Scheme 1. Molecular structure of TP-PDA, TTBP-PDA, TP-PMI and TP-PBI.
behaviour with H-aggregates as a common motif.[19] Many Results and Discussion
research groups have investigated the π-stacking of perylene-
based monoimides (PMIs) or -bisimides (PBIs) as a function of
The introduction of substituents in the bay-region of PDA
provokes a strong twist within the perylene ring and TP-PDA
becomes soluble in a wide range of organic solvents,[ such as
methanol (MeOH), dichloromethane (DCM), tetrahydrofuran,
toluene and acetone. Remarkably enough, when the red solution
of TP-PDA in DCM (10-3 M) was diluted with MeOH (5×10-6 M),
the color turned to yellow after several hours (inset in Figure 1).
Recovering the sample and re-dissolving it in DCM gave back
the original red color (Figure 2A).
MALDI-TOF-MS spectra of TP-PDA in MeOH pointed toward
unobstructed TP-PDA and excluded a chemical transformation
28]
[
[
a]
b]
B. Lü, S. You, P. Li, Prof. M. Yin, State Key Laboratory of Chemical
Resource Engineering, Beijing Laboratory of Biomedical Materials,
Beijing University of Chemical Technology, Beijing, 100029, China.
Email: yinmz@mail.buct.edu.cn
Prof. C. Li, Prof. K. Müllen, Institute of Physical Chemistry,
Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128
Mainz, Germany; Max-Planck-Institute for Polymer Research,
Ackermannweg 10, 55128 Mainz, Germany, Email: muellen@mpip-
mainz.mpg.de
Supporting information for this article is given via a link at the end of
the document.
(Figure S2), instead the color change must be attributed to the
reversible formation of supramolecular assemblies. For the sake
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be described as pre-equilibrium[13] and the formation of
of comparison, TTBP-PDA, TP-PMI and TP-PBI (Scheme 1)
were synthesized and investigated under the same conditions.
equilibrium H-aggregates. According to the previous
works,9-13 it can be concluded that the initial kinetically form
Similar assembly phenomena were observed in
a MeOH
solution of TTBP-PDA that contains two carboxydianhydride
groups, but not in a MeOH solution of TP-PMI or TP-PBI (Figure
S3), suggesting the importance of two carboxydianhydride
groups for the formation of supramolecular assemblies in MeOH.
In order to explore the underlying growth mechanisms, optical
spectra were recorded in DCM and MeOH at 283K (5×10-6 M)
is supposed to be disassemble at first, and there are
interplay and balance between the disassembly and self-
assembly into final H-aggregates. The titration experiments
were performed to gain the information on this aggregation
process and to study the solvent effect (Figure 3). A stock
solution of TP-PDA in MeOH (2×10-5 M) or DCM (2×10-5 M)
was prepared. The MeOH solution was titrated into the
DCM solution to form a DCM/MeOH mixture. The ratio of
DCM/MeOH was thus changed from 100:1 to 1:4. At the
low amount of MeOH, there was no obvious change in the
spectra. When the ratio of DCM/MeOH was increased up to
(Figure 1). It appeared that the absorption and emission
maxima had large blue-shifts ( ≈ 80 nm) which can readily
explained by the formation of H-aggregates.[29,30] We also
measured the optical properties of TP-PDA in other solvents, but
no similar blue-shifts were observed (Figure S4), indicating that
this phenomenon was depended on solvents used.
5
:1, the monomer TP-PDA began to aggregate into trapped
product since sufficient MeOH was needed to initiate
aggregation. The MeOH/DCM ratio affects the
thermodynamic equilibrium between the monomer and the
final H-aggregate.
Figure 3. UV-Vis absorption spectra of titration experiments.
Figure 1. UV-vis and fluorescence spectra of TP-PDA in (A) DCM, (B) MeOH
at the concentration of 5×10-6 mol/L. Inset: the photographs of TP-PDA in (A)
DCM, (B) MeOH.
The time dependent evolution of the color changes was
monitored by the spectral changes (Figure 2B). When the
solvent was switched from DCM (10-3 M) to MeOH (2×10-5
M), the absorption maxima shifted from 576 nm to 551 nm
immediately, corresponding to monomer peaks of TP-PDA
in DCM and MeOH, respectively. Within 4 minutes, the
absorption maxima of TP-PDA in MeOH revealed a blue
shift from 551 nm to 536 nm and then remained stable for a
few minutes due to the formation of kinetically trapped
aggregation.[14] Then the intensity of the peak at 536 nm
revealed a gradual decrease until stable. This process can
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Scheme 2. Self-assembly mode of TP-PDA in MeOH.
Figure 2. (A) Formation and transformation of supramolecular assembly of TP-PDA. (B) UV-visible spectra of TP-PDA in MeOH at 283K (concentration: 2×10-5 M).
(C) SEM image of TP-PDA H-aggregates.
F
(Ф =68%), obviously a result of aggregation-induced
In order to monitor the aggregation process in MeOH, in-
situ dynamic light scattering (DLS) was employed.[31,32] The
quenching effects.[33,34]
We deduce from the complex kinetic profile that there is
interplay between two states involving the initially trapped
aggregation and the final H-aggregates. In order to further
explore this complexity, we investigated the spontaneous
transformation of TP-PDA monomer to TP-PDA H-
aggregate. TP-PDA showed a relatively short trapping time
initial diameters of aggregates in MeOH were approximately
100 nm (Table S1), and then increased with time up to
approximately 300 nm. The morphology of the obtained
aggregates was further evaluated using scanning electron
microscopy (SEM). TP-PDA formed a regular sphere with a
diameter of about 600 nm in MeOH when it reached the
equilibrium H-aggregate state (Figure 2C). Interestingly,
the growth process could also be observed by in-situ SEM,
the spheres with diameters of 100-400 nm formed at
various time (Figure S5) upon fast evaporation of the
solvent. This observation is consistent with the DLS result
and supports the existence of a ‘pre-equilibrium’ as
illustrated by Scheme 2. The aggregate morphologies of
TP-PDA in DCM, acetone or tetrahydrofuran appeared as
irregular bulk phases (Figure S6), again, indicating the
important role of the solvent in regulating the assembly
process. The photoluminescence quantum yield (PLQY) of
(
the TP-PDA trapping time in MeOH was measured at a
concentration of 4×10-5 M at 283 K, Figure 4A). Under this
condition the final equilibrium H-aggregate of TP-PDA was
achieved after 1200 minutes, while the absorption peak
remained 20 minutes at 536 nm due to the trapping process
of TP-PDA monomer in MeOH (Figure 4B). During the
measurements, the transformation from TP-PDA monomer
to TP-PDA H-aggregate was accelerated by reduced
concentration and increased temperature properly and
could be completed even within several minutes. As shown
in Figures 4C and 4D, the H-aggregate of TP-PDA in
MeOH at a concentration of 1×10-5 M was achieved within
F
TP-PDA in DCM (Ф =76%) was higher than that in MeOH
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6
0 minutes at 288K. Thus, a higher temperature led to a
as solvent. The latter is non-protic, but has weak solvating
power. No similar blue shift was observed in dibutylether (Figure
S8), which indicated the existence of solvophobic interactions.
The striking feature in Fourier transform infrared (FTIR)
spectrum of TP-PDA in MeOH (Figure S9) was a stretching
frequency at ν(C=O) = 1680 cm-1 corresponding to a hydrogen-
bonded carbonyl group, indicating the existence of hydrogen
bonding between TP-PDA and MeOH molecule.[38] According to
previous reports, the aggregation could be destroyed by stimuli
faster H-aggregation process in MeOH (Figure 4E).
such as temperature,[13,14] concentration[39] and acid-base[40,41]
Here we tried to disintegrate the hydrogen-bonded
.
-
6
supramolecular structure of TP-PDA in MeOH (5×10 M) by
varying the pH through the addition of NaOH (1 M) or HCl (1 M).
When the pH of the solution decreased to 2, the color changed
to red. In contrast, when the pH value was adjusted to pH 7, the
solution returned to yellow and exhibited a yellow fluorescence
(Figure S10). Alkaline solutions were not considered because
perylene tetracarboydianhydrides are unstable under these
conditions. When exciting the chromophore at 520 nm, a new
peak at 600 nm appeared only under acidic conditions (pH=2) as
seen by the fluorescence spectra of TP-PDA (Figure S11). This
can be attributed to the disintegration of H-aggregate and the
emergence of fluorescent TP-PDA monomer under acidic
conditions. The absorption peak of the nanospheres was blue-
shifted in comparison with that of monomeric TP-PDA, indicating
that in H-aggregates the TP-PDA molecules overlap with a face-
to-face stacking.[
39]
The internal structure of self-assembled
Figure 4. (A) Time course of transformation from TP-PDA monomer to TP-
nanostructures of TP-PDA was also investigated by X-ray
diffraction (XRD) analysis (Figure 5).
-
5
PDA H-aggregate at 283 K (concentration: 4×10 M). (B) Constant plots of
absorbance at the given wavelength as a function of time (A). (C) Time course
of transformation from TP-PDA monomer to TP-PDA H-aggregate at 288 K
-
5
(
concentration: 1×10 M). (D) Plots of absorbance at the given wavelength as
a function of time (C). Time course of the aggregate formation in MeOH
−
5
(
2×10 M) at different temperatures (E) and at different concentrations (298 K)
F).
(
Moreover, the H-aggregation time is dependent on the
concentration (c ) of TP-PDA since a higher c results in a
T T
longer aggregation time (Figure 4F). This concentration-
dependent behaviour is consistent with that of a previously
reported porphyrin-based system, in which the monomers are
trapped as off-pathway aggregates.[ The transformation of TP-
PDA monomer to TP-PDA H-aggregate occurred after a trapping
time in accordance with a nonlinear sigmoidal transition (Figure
13]
4
E and 4F). This kinetic profile is characteristic of an
autocatalytic (or self-replication) process including a nucleation
and elongation processes.[13,14,35-37] It is noteworthy that the
Figure 5. X-ray diffraction patterns of the nanostructured TP-PDA from
methanol (black), from DCM (red) and none on glass sheets
transformation from TP-PDA monomer to TP-PDA H-aggregate
can be tuned or accelerated by mechanical stir, adding an
aliquot of TP-PDA H-aggregate solution, or increasing
As shown in Figure 5, two strong peaks at 0.35 and 0.71 nm
were observed in the XRD curve of TP-PDA in MeOH, but no
peak can be detected in DCM. It was reported that the π-π plane
distance ranged from 0.334 to 0.355 nm. The peak of 0.35 nm
could be assigned to the distance of the single-layer of π-
temperature (Figure S7). Given the unique
monomeric to H-aggregated TP-PDA in MeOH with time for ca.
200 minutes, the trapping time can be set to more than 20
evolution of
1
−
5
minutes at an initial concentration of 4×10 M at 283 K in MeOH.
It appears reasonable that TP-PDA aggregation is dominated
stacked perylene and the peak at 0.71 nm could be assigned to
the distance of double-layer of π-stack.[
42]
These results
by particularly strong π–π stacking together with solvophobic
demonstrated that π–π stacking and hydrogen bond in protic
solvents play an important role in the regulation of TP-PDA
aggregates in MeOH.
interactions and hydrogen bonding in protic solvents.[20] In order
to verify this hypothesis, we considered the role of dibutylether
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Conclusions
Keywords: Perylene tetracarboxydianhydride, Methanol,
Supramolecular assembly, Nano-size, Enlarged nanospheres
In conclusion, we have described the supramolecular assembly
of TP-PDA in MeOH. TP-PDA can self-assemble into regular
nanospheres that grow with time until the formation of
equilibrium H-aggregates, as revealed by DLS, SEM and UV-
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a kinetically
[
trapped assembly with rapid transformation into the
a
,
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TP-PDA, but also inspires us to explore other kinetically trapped
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[
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[
Acknowledgements
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This work was financially supported by the National Natural
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Entry for the Table of Contents (Please choose one layout)
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[
a]
[a]
A perylene tetracarboxydianhydride
derivative TP-PDA self-assembles
Baozhong Lü , Shusen You , Pengyu
[
a]
[b]
[b]
Li , Chen Li , Klaus Müllen and
Meizhen Yin[
a]
into
well-defined
nanospheres
through an autocatalytic process. The
π–π stacking, hydrogen bond and
solvophobic interactions play an
important role in the formation of
nanostructures. This study presents a
Page No. – Page No.
Kinetically trapped supramolecular
assembly of perylene dianhydride
derivative in methanol: optical
spectra, morphology and
mechanisms
new
kinetically
trapped
supramolecular assembly that can be
easily ignored due to the short
trapping
time
of
common
experimental timescales.
This article is protected by copyright. All rights reserved.