Near-Infrared-Emissive Amphiphilic BODIPY Assemblies Manipulated by Charge-Transfer Interaction: From Nanofibers to Nanorods and Nanodisks

Article abstract of DOI:10.1002/asia.201701323

A novel near-infrared (NIR)-emissive amphiphilic BODIPY derivative, BBDP, was successfully prepared and thoroughly characterized. The photophysical properties in various organic solvents and THF/H₂O mixtures with different fractions of water were investigated. BBDP self-assembled into nanofibers in a water environment owing to its amphiphilic properties. Through charge-transfer interactions, BBDP co-assembled with a perylene bisimide derivative, PBI, and a viologen derivative, MV, to generate two superamphiphiles. These two superamphiphiles were able to aggregate in water media at appropriate concentrations. The BBDP–PBI charge-transfer complex formed nanorods, whereas the BBDP–MV aggregates expressed a disk-like morphology. This research paves the way for us to manipulate the morphology of dye assemblies.

Full text of DOI:10.1002/asia.201701323

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Near-Infrared Emissive Amphiphilic BODIPY Assemblies
Manipulated by Charge-Transfer Interaction: From Nanofibers to
Nanorods and Nanodisks
Authors: Guichao Kuang, Jiafu Yin, Yi Hu, Huan Wang, Zhong Jin, and
Yi Zhang
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Chemistry - An Asian Journal
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Near-Infrared Emissive Amphiphilic BODIPY Assemblies
Manipulated by Charge-Transfer Interaction: From Nanofibers to
Nanorods and Nanodisks
Jia-Fu Yin,[ab] Yi Hu, Huan Wang, Zhong Jin, Yi Zhang, and Gui-Chao Kuang*
[c]
[a]
[c]
[b]
[a]
Abstract: A novel near-infrared (NIR) emissive amphiphilic BODIPY
derivative BBDP has been successfully prepared and thoroughly
characterized. The photophysical properties in various organic
as nanowires, nanotubes, nanoribbons, and so on.[26-30]
Sophisticated topological morphologies are commonly attributed
to the complicated molecular structures. However, there are few
work referred to tuning the amphiphilic NIR emissive BODIPY
derivatives self-assembly by noncovalent driving forces.
2
solvents and THF/H O mixtures with different fractions of water were
both investigated. BBDP could self-assemble into nanofibers in the
water environment due to the amphiphilic property. By utilizing the
charge-transfer interaction, BBDP could co-assemble with perylene
bisimide derivative (PBI) and viologen derivative (MV) respectively to
generate two superamphiphiles. Such two superamphiphiles were
able to aggregate in water media at appropriate concentration. BBDP-
PBI charge-transfer complex formed nanorods while BBDP-MV
aggregates expressed disk-like morphology. This research paves a
new way for us to manipulate the dyes assemblies’ morphology.
Charge-transfer interaction is a sort of typical noncovalent force,
which occurs between electron rich molecule and electron
deficient molecule.[31-35] Superamphiphiles induced by charge-
transfer interaction could be obtained by simply mixing the donors
with acceptors in the solvent.[ In this regard, this strategy has
shown advantages to avoid complicated and tedious synthesis.
Since the host-stabilized charge transfer self-assembly concept
established by Kim et al,[37] significant progresses have been
made by Zhang and co-workers in the field of superamphiphiles
charge-transfer assembly. Versatile nanostructures have been
36]
realized by rational designed intermolecular charge-transfer
interaction.[38-44] On the other hand, functional or responsive parts
Introduction
could be integrated with target molecules via charge-transfer
interaction, so that the novel assemblies with definitely distinct
shapes and functional groups could be obtained.[44] Due to the
rapid expansion of biomaterial and medicinal chemistry, more and
more NIR emissive materials are in highly urgent. We are
particularly engrossed in utilizing charge-transfer strategy to
construct various nanoscopic architectures with NIR amphiphilic
molecules.
Amphiphilic aggregates with well-defined architectures have
drawn considerable attention in the past decades because of their
potential application in nanotechnology, biochemistry, and
[
1-8]
material science.
Among them, near-infrared (NIR) emission
dyes assemblies play important roles in the fields of
nanomaterials and biomedicine.[9-15] Boron−dipyrromethenes
(
BODIPY) derivatives have raised as star dye molecules because
of their excellent fluorescent properties with high quantum yields
and outstanding light stability.[15-17] Furthermore, structural
modifications on the BODIPY dyes could significantly alter the
photophysical properties. NIR emissive BODIPY derivatives could
be achieved by extensive aromatic ring fusion or aza-nitrogen
introduction at the meso-position.[18-25] Amphiphilic BODIPY
derivatives with hydrophobic planar aromatic ring and hydrophilic
parts obtained the potential to aggregate in the aqueous solution,
resulting in the formation of versatile topological structures such
To address the above-mentioned consideration, a novel NIR
emission BODIPY derivative (BBDP) has been constructed. In
order to realize the NIR emission, two pyrene units were attached
to the BODIPY core to extend the conjugated architecture. Three
oligo (ethylene glycol) (OEG) chains were introduced as the
hydrophilic parts. Such an amphiphilic BODIPY derivative which
possessed both hydrophobic part and hydrophilic unit was able to
self-assemble in aqueous solution. Pyrene moieties are typical
electron-rich units, which behave as electron donors to provide
electron to the electron acceptors. Perylene bisimide derivative
[
a]
J.- F. Yin, H. Wang, Prof. Dr. G.- C. kuang
State Key Laboratory of Power Metallurgy
Department of Polymer Materials and Engineering,
Central South University
(
PBI) and viologen derivative (MV) are well-reported electron-
poor molecules in charge-transfer system.[ We hope to obtain
two co-assembly complexes between BBDP and the above two
acceptors by employed charge-transfer interaction. Then the
obtained charge-transfer complexes could assemble in the water
media and display distinct morphologies.
31]
Changsha, Hunan 410083, China
E-mail: gckuang@csu.edu.cn
[
b]
c]
J. -F. Yin, Prof. Dr. Y. Zhang
College of Chemistry and Chemical Engineering Department,
Central South University
Changsha, Hunan 410083, China.
Y. Hu, Prof. Dr. Z. Jin
Results and Discussion
[
Key Laboratory of Mesoscopic Chemistry of MOE,
School of Chemistry and Chemical Engineering,
Nanjing University
Photophysical properties and aggregation behaviours of
BBDP
Nanjing, Jiangsu 210093, China
Supporting information for this article is given via a link at the end of
the document.
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BBDP has been prepared according to the synthetic routes
(
Scheme 1). Formyl-modified OEG dendrons 1 followed a classic
synthetic pathway of BODIPY derivatives to afford the target
molecule 2.[
45]
Then, compound 2 underwent Knoevenagel
reaction with 1-pyrenecarboxaldehyde to generate the final
product BBDP.[26] Perylene bisimide derivative (PBI) and viologen
derivative (MV) were obtained according to the literature.[46, 48]
More details about the synthetic processes and characterization
data were described in the Experiment Section.
Figure 2. UV-vis (a) and fluorescence spectra (b) of BBDP with
different water fractions in THF/H
Tyndall effect of BBDP assemblies in THF/H
M).
employed to trace the aggregation behaviours of BBDP in
THF/H O mixture with different fractions of water. The absorption
2
O mixture (c = 10 M); (c)
2
O mixture (c = 10

2
intensity decreased sharply accompanied by the hypsochromic
shifts of the absorption wavelength when the fraction of water
reached to 80% (Figure 2a). At the same time, the fluorescent
emission decreased gradually and fully quenched eventually after
further water addition (Figure 2b). The fluorescence quenched
effect was assigned to the strong , -stacking interactions of the
bent-shaped rod building blocks and the existence of hydrophobic
interactions during the formation of nanoaggregates.[30, 49] The
above two evidences were sufficient to prove that the BBDP
Scheme 1. (a) Synthetic procedures for BBDP; (b) Structures of
PBI and MV studied in the present work.
The photophysical properties of BBDP in various organic
solvents were investigated by UV-vis and fluorescence (FL)
spectroscopy (Figure 1). As for the UV-vis spectra, the absorption
band located between 680-710 nm and a shoulder around 650
nm were assigned to the S0-S1 transition of the delocalized -
conjugated core and vibrational structure, respectively. The
emission band of BBDP was located at NIR range on account of
the extensive conjugated pyrene-BODIPY architecture. Besides,
BBDP showed small stokes shifts in various solvents (less than
molecules have formed H-type aggregates in the THF/H
mixture.[28, 30] Besides, light opalescence and obvious Tyndall
effect have been observed in THF/H O mixture, which could
2
O
2
further demonstrate the formation of nanoaggregates (Figure 2c).
Dynamic light scattering (DLS) results revealed that the
hydrodynamic diameters of the BBDP aggregates were not
related with the concentration. The average size was calculated
to be 1.2 m (Figure S7).
3
0 nm) indicating that there was weak intramolecular donor-
acceptor interaction in the ground state.[45] More information about
the photophysical data of BBDP was summarized in Table S1
(
Supporting information).
Figure 1. Normalized absorption and emission spectra of BBDP
in different solvents (c = 10 M). DMSO = dimethyl sulfoxide,
CH
tetrahydrofuran and DCM = dichloromethane.
Due to the classic amphiphilic characteristics, BBDP could self-
assemble into NIR supramolecular aggregates in aqueous
solution due to the driving forces of hydrophobic interactions and
3 3
OH = methanol, ACN = acetonitrile, CHCl = chloroform, THF
=
Figure 3. (a, b, c) SEM images with different magnification of
BBDP aggregates in aqueous solution (c = 6 M); (d) AFM
morphology image of BBDP aggregates in aqueous solution (c =
, -stacking interactions. UV-vis and FL measurements were
4
M); (e) Section analysis of the nanoaggregates.
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1
Scanning electron microscopy (SEM) experiments were
performed to investigate the morphologies of the BBDP
supramolecular assemblies in aqueous solution (Figure 3a, b, c).
Interestingly, great deals of wire-like nanostructures have been
observed for the aggregates in water media. In addition, these
nanofibers possessed relatively high length/diameter ratios. The
length of the nanofibers is up to several micrometers and the
diameter of the nanoassemblies is about several dozens of
nanometers. Atomic force microscopy (AFM) image also revealed
the existence of the nanofibers on the mica surface (Figure 3d).
AFM image analysis was applied to collect the height information
of the obtained nanofibers. As shown in the Figure 3e, the height
of these nanofibers was measured to about 40 nm while the
diameter of the nanowires was around 100 nm (Figure 3e). To
gain a further investigation of the formation mechanism of
nanofiber morphology, we speculated that the hydrophilic OEG
chains were exposed to the highly polar water while the planar
hydrophobic moieties preferred to form H-type assembly for the
minimization of free energy. In this way, the nanoaggregates
presented fiber-like morphology. Fluorescent microscopy images
also revealed the existence of wire-like structures. Due to the NIR
properties of the BBDP aggregates, NIR emissive nanofibers
could be obtained from the fluorescent microscopy images
Figure 4. (a) H NMR spectra of BBDP (c = 2 mM), BBDP-MV
(molar ratio = 1:2, cBBDP = 2 mM) co-assembly complex, MV (c =
(
Figure S10).
Charge-transfer interaction and aggregates morphology
The NIR emissive BBDP possessed the potential to co-
assemble with electron-poor molecules by charge-transfer
interaction due to the existence of pyrene moieties. We noticed
that the charge-transfer strategy might be a feasible way to
manipulate the nanostructures of the NIR aggregates with high
efficiency. In this regard, PBI and MV were selected as electron-
deficient acceptor molecules, while BBDP behaved as electron-
rich donor molecule. As well known, pyrene units could initially
assemble with viologen or perylene bisimide groups with a molar
ratio of 1:1 to form supramolecular complexes driven by charge-
1
2
mM) in THF-d
8
/D
2
O mixture. (b) 2D H NMR NOESY spectrum
[
31, 32, 39, 44, 47]
of BBDP-MV (molar ratio = 1:2, cBBDP = 2 mM) complex in THF-
/D O (v/v, 5:1) mixture.
transfer interaction.
Considering the MV showing
d
8
2
stronger electron-withdrawing ability than PBI, we are wondering
whether any morphology variation would be achieved by adding
different acceptor molecules.
Nuclear Overhauser Effect spectroscopy (NOESY) tests have
been exploited to further elaborate the charge-transfer complex.
The distance between donor and acceptor molecule would be
shorten to less than 5 Å by charge-transfer interaction.[
Therefore, the NOE signals could be observed upon the formation
of charge-transfer complex. 2D 1H NMR NOESY spectrum of
The co-assembly behaviour between BBDP and MV was
39]
1
investigated by H NMR measurements. The peaks between 8.9-
7
7
.9 ppm were all ascribed to the pryene units, while the peaks at
.46 and 7.14 ppm were ascribed to protons on the pyrrole rings
3
BBDP and PBI (molar ratio is 1:2) in CDCl was collected. As
of BBDP. After MV addition, dramatic peaks upfield shift in the
low field region was observed. As shown in Figure 4a, the
resonance of the protons on BBDP and MV (molar ratio is 1:2)
showed upfield shifts due to the formation of charge-transfer
complex. This phenomenon may be attributed to the ring-current
shielding effects induced by the strong , -interaction between
BBDP and MV. This result was consistent with the previous
reports by other researchers. [32, 39, 40] 1H NMR measurements of
3
BBDP and PBI complex was performed in CDCl solvent (Figure
shown in the Figure S2, the correlations between the protons of
BBDP and PBI were observed, indicating the formation of
supramolecular complex. MV was a sort of electron deficient
group which obtained higher electron-withdrawing capacity than
PBI. When MV was mixed with BBDP with a molar ratio of 2:1 in
THF-d
8
/D
2
O mixture, much stronger correlations have been
1
detected and more correlations spots could be found in the 2D H
NMR spectrum (Figure 4b). This effect was mainly associated
with the distinction of the electron-withdrawing ability. UV-vis and
FL spectrometry have been employed to provide
S1). The chemical shifts of the supramolecular complex follow the
same trend that the signal peaks in aromatic regions up-field
1
shifted. H NMR information has provided direct evidence to the
formation of charge-transfer complexes.
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Figure 5. (a, b) SEM images and (c, d) AFM images with individual height of the BBDP-PBI nanoaggregates (molar ratio = 1:2, cBBDP
6 M) in THF/H O mixture; (e, f) SEM images and (g, h) AFM images with individual height of the BBDP-MV nanoaggregates
molar ratio = 1:2, cBBDP = 6 M) in THF/H O mixture.
=
2
(
2
aggregation size of about 667 nm (PDI = 0.212) (Figure S9).
Furthermore, the hydrodynamic diameters of the BBDP-PBI
aggregates were founded to increase with the enhancement of
the concentration. However, the aggregates size showed little
dependence on concentration for BBDP-MV system.
more photophysical information of the two charge-transfer
complexes (Figure S3, S4). Beyond our expectation, little change
of absorption spectra occurred and emission intensity of the
obtained charge-transfer complex only showed a faint decrease.
We proposed that the BODIPY derivatives were a range of stable
fluorescent materials, which obtained the capacity to withstand
the external factors. Hence, two novel charge-transfer complexes
with NIR emission have been realized by utilizing the charge-
transfer strategy.
Considering the amphiphilic nature of the as-prepared two
charge-transfer complexes, we speculated that novel NIR
nanoaggregates could be realized in the aqueous media. In an
effort to elucidate the architecture of the resulting nanoassembly,
SEM and AFM imaging were performed at multiple locations
across the samples. As we expected, BBDP-PBI
superamphiphile self-assembly displayed a typical nanorod
suprastructure from the SEM images (Figure 5a, b). These
nanorods obtained external diameter of about 50 nm while the
length was up to more than 1 m. AFM characterizations also
demonstrated the formation of rod-like structures, which was
consistent with the SEM results (Figure 5c). This observation
should be attributed to the monolayer arrangements of the BBDP-
PBI charge-transfer complex. To further investigate the
morphology, Nanoscopy analysis software were employed to
collect the more information of the aggregates. The height of the
nanorods was around 25 nm and the lateral size of the nanorods
was about 80 nm, which was in accordance with the SEM results
above (Figure 5d). In contrast, BBDP-MV complex nanoassembly
expressed different morphology. Numerous nanodisks with
uniform size have been detected in the SEM images (Figure 5e,
f). The lateral size of the nanoaggregates was around 200 nm.
Similar nanostructures could be obtained from the AFM results,
which could further confirm the generation of nanodisks. AFM
height analysis has revealed that these nanodisks possessed a
rather uniform height. These nanodisks were found to obtain an
average height of 34 nm while the diameter of the nanodisks was
around 200 nm (Figure 5 g, h). As indicated by fluorescent
microscopy images, the BBDP-MV aggregates expressed
nanodisks morphology and presented red emission under the
excitation light with a specific wavelength while BBDP-PBI could
self-assemble into nanorods (Figure S11, S12).
By utilizing the photophysical methods, the aggregation
behaviours of the above two charge-transfer system could be
observed directly in the water environment. As for the BBDP-MV
charge-transfer complex, the absorption band around 700 nm
declined with the enhancement of the water fraction (Figure S5).
Moreover, the absorption intensity decreased dramatically
accompanied by 40 nm hypsochromic shifts when the water ratio
reached to 80 %. During the aggregation procedure, the emission
intensity suffered a sharply diminishment and fully quenched in
the end. Hence, it could be seen that the BBDP-MV formed H-
Type aggregates in the aqueous media. By integrating with PBI
molecules via the charge-transfer noncovalent interaction, BBDP-
PBI possessed higher hydrophobic ratio than the single BBDP.
Thus, BBDP-PBI might be more inclined to assemble at the same
concentration. As shown in the Figure S6, The absorption
intensity began to drop upon the initial addition of water to the
system. When the water fraction reached to 70%, the absorption
intensity declined to almost half of the original intensity. Both the
absorption and emission band expressed obvious bathochromic
shifts while the fluorescent emission was quenched after the
water addition. We speculated that H-Type and J-Type
aggregation cooperated with each other in the system. The
nanoparticle formation was further confirmed by DLS
measurements. The hydrodynamic diameter of the BBDP-MV
(CBBDP = 6 M) aggregates was calculated to 250 nm with a
relatively low polydispersity index (PDI = 0.243) (Figure S8). The
BBDP-PBI (CBBDP = 6 M) assemblies possessed a much larger
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nanoassemblies, these NIR materials might show potential
applications in many fields. By integrating with specific functional
groups via charge-transfer interaction, specific applications were
able to be achieved. Further work on this aspect to design
functional materials based on NIR BODIPY derivatives is ongoing
in our laboratory.
Experimental Section
1. Materials
All reagents were purchased form commercial sources and used without
further purification unless otherwise stated. Solvents were dried by fluxing
under nitrogen with calcium hydroxide. All the reactions stated in this paper
were performed in dried glassware under nitrogen atmosphere. Analytical
thin-layer chromatography (TLC) was performed on precoated silica gel
plates (0.4-0.5 mm thick). Column chromatography was performed on
silica gel (200-300 mesh) as the stationary phases. Deionized water was
obtained from the ultrapure water system, HITRCH Smaret-S15.
Scheme 2 (a) Schematic illustration for the formation of
nanofibers from BBDP; (b) nanorods from the co-assembly of
BBDP and PBI; (c) nanodisks aggregates from the co-assembly
of BBDP and MV.
2. Instruments and Measurements
With the different self-assembly morphologies in hand, a model
was proposed (Scheme 2). BBDP possessed large planar rigid
structures underneath while flexible OEG Chains were placed on
the top. The hydrophobic planar blocks were inclined to assemble
to generate the core of the nanofibers and the hydrophilic OEG
chains were exposed to the exterior water environment. Hence,
fiber-like morphology could be obtained from the SEM and AFM
images. After the formation of charge-transfer co-assembly
complexes, the self-assembly behaviours made difference so that
the nanoaggregates presented distinct morphologies. As for the
BBDP-PBI superamphiphile, two PBI were attached to the BBDP
due to the existence of charge-transfer interaction. In this way, the
obtained superamphiphile possessed two hydrophilic parts. To be
different with the aggregation behaviour of BBDP, the BBDP-PBI
superamphiphiles tended to lay bare the two hydrophilic parts at
both end to the water media, while the hydrophobic parts piled
together to promote the water solubility. Then the nanorods could
be formed eventually. The BBDP-MV superamphiphile expressed
similar architecture with the BBDP-PBI complex. The distinction
of the morphology of the nanoaggregates may be associated with
the better water solubility or smaller size of the MV groups.
1H and 13C NMR spectra were recorded on Bruker Avance spectrometer
at 400 and 100 MHz respectively under 298 K. All Chemical shifts are
reported in parts per million (ppm) using tetramethylsilane (TMS) as an
internal reference. A Hitachi U-5100 spectrometer was used to measure
the UV-vis absorption spectra. Fluorescence emission spectra were
recorded on Hitachi F-2700 spectrometer. High-resolution mass
spectrometry experiments were carried out with a Bruker Daltonics Apex
IV spectrometer. SEM images were obtained from a JSM 6390LV
microscope. AFM experiments were carried out with a Bruker Nanoscope
VIII Multi-Mode microscope. The sample was prepared by pipetting aliquot
of the corresponding solution on the mica surface and dried under room
temperature. Nanoscope analysis software was exploited to investigate
the AFM images. Fluorescent microscopy images were obtained from the
OLYMPUS IX83 fluorescent microscopy. Hydrodynamic diameters of the
nanoaggregates at different concentration were determined at 298 K on
ZEN3600 MALVERN by Dynamic light scattering (DLS). X-ray diffraction
(XRD) patterns of the samples were measured on Advance D8.
3. Construction of amphiphilic assemblies
Preparation of BBDP aggregates: BBDP was dissolved in tetrahydrofuran
to form a solution with a concentration of 2.4×10-5 mol/L. The deionized
water (3 mL) was added dropwise into the above BBDP solution (1 mL) to
induce the aggregate formation accompanied by stirring with a relatively
low speed of 200 r/min. Kept stirring for 2 h and then let it stand still of 12
h.
Conclusions
Preparation of BBDP-PBI aggregates: The sample was prepared in the
same manner except the initial tetrahydrofuran solution (BBDP: PBI = 1:2,
C
In summary, a novel NIR emissive BODIPY derivative BBDP
has been prepared. Such an amphiphilic structure possessed the
potential to self-assemble in the aqueous solution. By utilizing the
charge-transfer interaction, BBDP could be transferred into two
novel superamphiphiles that could form nanoaggregations in the
aqueous media. The individual BBDP could self-assemble into
nanofibers while the BBDP-PBI complex aggregates expressed
nanorod morphology. Furthermore, numerous nanodisks with
uniform size could be observed from the SEM and AFM images
of BBDP-MV complex assemblies. Therefore, it is available for us
to achieve the morphology transition by introducing the charge-
transfer interaction. Considering the NIR properties of the three
BBDP =2.4×10-5 mol/L).
Preparation of BBDP-MV aggregates: The sample was prepared in the
same manner except the initial tetrahydrofuran solution (BBDP: MV = 1:2,
BBDP =2.4×10-5 mol/L).
C
4. Synthesis and characterization
Synthesis of 2: Compound 1 was synthesized according to the literature.
[
45]
Compound 1 (700 mg, 0.97 mmol) and 2-methylpyrrole (162 mg, 2.0
mmol) were dissolved in anhydrous dichloromethane (DCM) 150 mL. Two
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drops of trifluoroacetic acid (TFA) were added to the mixture as the catalyst.
The reaction was performed under room temperature and stirring was kept
for 12 h under nitrogen atmosphere. After that, 2, 3-dicyano-5, 6-
dichlorobenzoquinone (DDQ) (220 mg, 0.97 mmol) was added to the
system and kept stirring for another 12 h. N, N-diisopropylethylamine
Acknowledgements
This work was supported by State Key Laboratory of Powder
Metallurgy, Central South University, and the National Natural
Science Foundation of China (NSFC No. 21204047).
(DIEA, 2 mL) was added under ice bathing for 10 minutes. Boron trifluoride
diethyl etherate (BF .OEt , 4 mL) was added to the mixture and kept
3
2
stirring for 8 h. After the reaction was over, the solvent was evaporated
under reduced pressure. The crude product was purified by silica gel
Conflicts of interests
chromatography with DCM/CH
compound 2 (300 mg, 34%). H NMR (400 MHz , CDCl
3
OH (20:1, v/v) as eluents to afford
1
The authors declare no conflict of interest.
3
): δ = 6.78 (d, J =
4
.0 Hz, 2H), 6.74 (s, 2H), 6.26 (d, J = 4.0 Hz, 2H), 4.23 (t, J = 4.8 Hz, 2H),
.15 (t, J = 4.8 Hz, 4H), 3.52-3.81 (m, 42H), 3.36 (d, J = 6.9 Hz, 9H), 2.63
): δ = 156.85, 151.87, 139.61, 133.73,
29.96, 128.70, 118.99, 109.96, 72.12, 71.46, 70.34, 70.20, 70.14, 70.02,
4
(
Keywords: Near-infrared BODIPY derivative • Amphiphilic self-
assembly • Charge-transfer interaction • Morphology transition
s, 6H).13C NMR (100 MHz, CDCl
3
1
6
9.28, 68.70, 58.52. ESI-MS: Calcd. for
44 2 2 15
C H69BF N O K
[
1]
M. Vybornyi, A. V. Rudnev, S. M. Langenegger, T. Wandlowski, G.
Calzaferri, R. Haner, Angew. Chem. Int. Ed. 2013, 52, 11488-11493;
Angew. Chem. 2013, 125, 11702 –11707.
+
[M+K ],953.4396. Found: 953.4852.
Synthesis of BBDP:[26] Compound
pyrenecarboxaldehyde (100 mg, 0.44 mmol) and p-toluenesulfonic acid (p-
TsOH, 10 mg) were dissolved in the mixture of toluene (25 mL) and
piperidine (1 mL). Stirring was kept at 120 C for 2 h under the protection
2 (100 mg, 0.11 mmol), 1-
[
[
[
[
[
[
[
[
[
[
[
[
[
2]
3]
4]
5]
6]
7]
8]
9]
T. Fukui, S. Kawai, S. Fujinuma, Y. Matsushita, T. Yasuda, T. Sakurai,
S. Seki, M. Takeuchi, K. Sugiyasu, Nat. Chem. 2017, 9, 493-499.
X. Zhang, S. Rehm, M. M. Safont-Sempere, F. Würthner, Nat. Chem.
o
2
009, 1, 623-629.
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o
2
of N . After that, the temperature was reached to 150 C and the solvent
was evaporated into the dean stark apparatus. Then toluene (25 mL) and
piperidine (1 mL) were added to the system and the dryness process was
repeated for 6 times until the reagent was consumed. The crude product
was washed with water, dried over MgSO , filtered and evaporated. The
4
residue was subjected to column chromatography with DCM/CH
1
2
3
OH (10:1,
2
1
v/v) to afford a dark-green solid (40 mg, 27%). H NMR (400 MHz, CDCl
3
):
δ = 8.63-8.51(m, 6H), 8.26-8.03(m, 22H), 7.21 (d, J = 4.6 Hz, 2H), 7.01 (d,
J = 4.4 Hz, 2H), 6.87 (s, 2H), 4.30 (t, J = 5.2 Hz, 2H), 4.24(t, J = 5.0 Hz,
0
4
H), 3.91-3.53 (m, 42H), 3.35 (d , J = 12.2 Hz, 9H). 13C NMR (100 MHz,
4
CDCl
3
): δ = 154.92, 152.60, 140.12, 138.73, 136.53, 133.01, 132.07,
31.55, 130.89, 130.52, 129.75, 129.08, 128.20, 127.66, 125.88, 125.50,
25.11, 124.89, 122.52, 116.85, 110.62, 72.70, 72.04, 70.97, 70.76, 70.60,
9.86, 69.26, 59.12. ESI-MS: Calcd. for
377.5648. Found: 1377.6412.
1
1
6
1
1
78 2 2 15
C H85BF N O K
[M+K+],
2
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2
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0.40 g) were placed in an oven-dried three-neck flask. Imidazole (44.1
mmol, 3 g) and a catalytic amount of Zn(OAc)
The reaction mixture was heated to 160 C and kept stirring for 18 h under
the protection of N . After the reaction mixture was cooled down to room
2
2
were added to the system.
1
o
2
temperature, 100 mL deionized water was added and kept stirring for 20
minutes and 5% HCl was used to remove the residual imidazole. Then
extracted with DCM and collected the organic layer. Then the organic layer
[
[
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[
18] P. P. Goswami, A. Syed, C. L. Beck, T. R. Albright, K. M. Mahoney, R.
1
3
DCM/CH OH (20:1, v/v) to afford a red-brown solid (320 mg, 47%). H NMR
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3
(400 MHz, CDCl ): δ = 3.32 (s, 6H), 3.46-3.49 (m, 4H), 3.59-3.62 (m, 4H),
3786.
3
=
.64-3.66 (m, 4H), 3.74-3.76 (m, 4H), 3.87 (t, J = 6.00 Hz, 4H), 8.45 (d, J
8.08 Hz, 4H), 8.56 (d, J = 7.96 Hz, 4H).
[
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2
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1
product was obtained as a red powder (270 mg, 96%). H NMR (400 MHz,
2
D O): δ = 4.51 (s, 6H), 8.53 (d, J = 6.26 Hz, 4H), 9.06 (d, J = 6.32 Hz, 4H).
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Chemistry - An Asian Journal
10.1002/asia.201701323
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ab]
Yi Hu,[c] Huan Wang,[a]
Suprastructure of the nanoaggregates
could be regulated by introducing the
charge-transfer interaction. BBDP
could self-assemble into nanofibers in
water media. By utilizing the charge-
transfer interaction, BBDP could
interact with PBI and MV respectively
to fabricate two novel charge-transfer
complexes. Afterwards, the BBDP-
Jia-Fu Yin,[
Zhong Jin,[ Yi Zhang, and Gui-Chao
c]
[b]
Kuang*[a]
Near-Infrared Emissive Amphiphilic
BODIPY Assemblies Manipulated by
Charge-Transfer Interaction: From
Nanofibers
Nanodisks
to
Nanorods
and
PBI
nanoaggregates
expressed
nanorod morphology, while the BBDP-
MV complex self-assembled into
nanodisks.
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