C3-symmetrical cyano-substituted triphenylbenzenes for organogels and organic nanoparticles with controllable fluorescence and aggregation-induced emission

Article abstract of DOI:10.1002/ejoc.201400014

Fluorescent organic molecules with C₃-symmetry consisting of tris{2-cyano-2-[4-(dodecyloxybenzoylamino)phenyl]-1-ethenyl}phenylbenzene (CN-DBAPPBn, n = 1, 2, 3) were synthesized. It was observed that these compounds can spontaneously self-assemble into organogels in many organic solvents. Scanning electron microscopy (SEM), light microscopy, and fluorescence microscopy images of the air-dried gels showed the presence of either heavily entangled amorphous or fibrous structures, or rods. FTIR, UV/Vis absorption, excitation and emission spectra suggest that π-π interactions and H-bonding are the driving forces for the formation of the gel phases. Moreover, spherical or cubic fluorescent nanoparticles based on CN-DBAPPBn were prepared by using a reprecipitation method in a mixture of tetrahydrofuran and water. It is interesting that aggregation-induced emission behavior of CN-DBAPPBn was detected in both the gel phase and in the nanoparticle suspensions. The fluorescent molecular aggregates of CN-DBAPPBn with different architectures and emission properties fabricated by using these self-assembling methods could find potential applications in sensors and optoelectronic devices.

Full text of DOI:10.1002/ejoc.201400014

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FULL PAPER
DOI: 10.1002/ejoc.201400014
C3-Symmetrical Cyano-Substituted Triphenylbenzenes for Organogels and
Organic Nanoparticles with Controllable Fluorescence and Aggregation-
Induced Emission
Oudjaniyobi Simalou,[a,b,c] Ran Lu,*[a] Pengchong Xue,[a] Peng Gong,[a] and Tierui Zhang*[b]
Keywords: Aggregation / Colloids / Gels / Nanoparticles / Fluorescence
Fluorescent organic molecules with C3-symmetry consisting
of tris{2-cyano-2-[4-(dodecyloxybenzoylamino)phenyl]-1-
mation of the gel phases. Moreover, spherical or cubic fluo-
rescent nanoparticles based on CN-DBAPPBn were prepared
by using a reprecipitation method in a mixture of tetra-
hydrofuran and water. It is interesting that aggregation-in-
duced emission behavior of CN-DBAPPBn was detected in
both the gel phase and in the nanoparticle suspensions. The
fluorescent molecular aggregates of CN-DBAPPBn with dif-
ferent architectures and emission properties fabricated by
using these self-assembling methods could find potential ap-
plications in sensors and optoelectronic devices.
ethenyl}phenylbenzene (CN-DBAPPBn, n = 1, 2, 3) were syn-
thesized. It was observed that these compounds can sponta-
neously self-assemble into organogels in many organic sol-
vents. Scanning electron microscopy (SEM), light micro-
scopy, and fluorescence microscopy images of the air-dried
gels showed the presence of either heavily entangled
amorphous or fibrous structures, or rods. FTIR, UV/Vis ab-
sorption, excitation and emission spectra suggest that π–π in-
teractions and H-bonding are the driving forces for the for-
fields.[1–6] In particular, the development of π-gels is of great
importance in the fabrication of new functional soft materi-
als with special properties, including enhanced charge trans-
port, fluorescence enhancement, light-harvesting, two-pho-
ton absorption, and sensing.[5c,6,7a–c] It is well-known that
controlled optoelectronic properties of self-assemblies
based on π-conjugated gelators can be achieved through
changing the conjugation length,[1b] donor–acceptor
strengths,[7d] aliphatic groups,[8b] or system of hydrogen
bonding.[8c,8d] Although Smith and Rogers et al. have re-
ported studies in which the solvent modulates the level of
hierarchical self-assembly of organic gelators,[8a,8e] few re-
ports have focused on the effect of the solvent on the gela-
tion process, morphology, and photoelectronic properties of
π-gel systems. Herein, we designed new C3-symmetrical tri-
phenylbenzene-based fluorescent π-conjugated molecules
(CN-DBAPPBn) bearing cyano groups and long alkyl
chains (Scheme 1). It is interesting that these compounds
can form gels in many organic solvents, and we report that
the microstructures as well as the photophysical properties
of the gels can be modulated by the solvents. For example,
the gel of CN-DBAPPB3 obtained in either 1,2-dichloro-
benzene or toluene gave amorphous morphology and emit-
ted greenish light centered at ca. 501 nm, whereas the CN-
DBAPPB3 benzaldehyde gel was composed of right- and
left-handed helical fibers and emitted strong greenish-
yellow light at 520 nm; in 1,4-dioxane the gel of CN-
DBAPPB3 emerged as nanorods emitting greenish-blue
light located at 490 nm. Stable spherical or cubic nanopar-
ticles with emission at ca. 485, 491, and 484 nm for CN-
Introduction
In recent years, a great number of organic π-conjugated
molecules have been increasingly used in organic photonic
and electronic devices.[1] It has been found that the ordering
and orientation of the chromophores is useful for high per-
formance in devices. Although numerous ordered chromo-
phoric assemblies have been fabricated, the ability to conve-
niently control the molecular packing of π-conjugated units
remains elusive.[2] It is interesting that various 1D align-
ments of π-conjugated molecules leading to various archi-
tectures, such as fibers, rods, ribbons and so on, have so far
been constructed through supramolecular processes. Nowa-
days, low-molecular-weight organogels have attracted in-
creasing interest not only because the gelators can self-as-
semble into 1D ordered superstructures through noncova-
lent interactions, but also because they have potential appli-
cations in separation, catalysis, template synthesis, cosme-
tics, drug delivery, molecular electronics, and related
[a] State Key Laboratory of Supramolecular Structure and
Materials, College of Chemistry, Jilin University,
Changchun 130061, P. R. China
E-mail: luran@mail.jlu.edu.cn
http://chem.jlu.edu.cn/chemistry/index.php
[b] Key Laboratory of Photochemical Conversion and Optoelec-
tronic Materials, Technical Institute of Physics and Chemistry,
Chinese Academy of Sciences,
Beijing 100190, P. R. China
[c] Département de Chimie, Faculté Des Sciences, Université de
Lomé,
BP 1515, Lomé, Togo
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201400014.
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O. Simalou, R. Lu, P. Xue, P. Gong, T. Zhang
FULL PAPER
Scheme 1. Synthetic route to CN-DBAPPBn (n = 1, 2, 3).
DBAPPB1, CN-DBAPPB2, and CN-DBAPPB3, respec-
The gelation ability of CN-DBAPPBn was evaluated in
tively, were fabricated by using a reprecipitation method in several organic solvents (Table 1), and it was found that all
a mixture of tetrahydrofuran (THF) and water,[9] and aggre- the derivatives showed good gelation ability in aromatic sol-
gation-induced emission (AIE) was observed during the vents (benzene, toluene, p-xylene, 1,2-dichlorobenzene,
self-assembling process in both systems. Therefore, con- benzaldehyde, and bromobenzene), dichloromethane, and
trolled fluorescent emission can be realized by tuning the 1,4-dioxane. For example, CN-DBAPPB1 was insoluble in
microstructures of the assemblies based on CN-DBAPPBn toluene at room temperature, and a clear solution appeared
in different solvents, which is useful for the generation of when the mixture was heated to ca. 100 °C. Upon cooling
novel functional soft materials with desirable properties.
to room temperature, an immobile transparent rigid gel
(CGC = 0.5 wt./vol.-%) was readily formed within 2 to
5 minutes. In addition, CN-DBAPPB1 formed a stable,
opaque gel in dimethyl sulfoxide (DMSO), and dissolved
upon heating. However, it was difficult to dissolve CN-
DBAPPB3 completely in DMSO at high temperature, and
in this case an unstable gel was obtained. In N,N-dimethyl-
formamide (DMF), CN-DBAPPB3 formed an unstable gel,
whereas CN-DBAPPB1 and CN-DBAPPB2 were soluble.
CN-DBAPPB2 could gel chloroform at a CGC of ca.
12.5 wt./vol.-%, but CN-DBAPPB1 and CN-DBAPPB3 did
not. Moreover, all CN-DBAPPBn derivatives were virtually
insoluble in ethanol, methanol, and acetonitrile.
Results and Discussion
Synthesis, Gelation, and Self-Assembly of CN-DBAPPBn
The synthetic route to triphenylbenzene derivatives CN-
DBAPPBn is depicted in Scheme 1. First, the cyclization of
p-bromoacetophenone afforded compound 1 in a yield of
87%, which was converted into 1,3,5-tris(4-formylphenyl)-
benzene (2) by lithiation and formylation reactions. Com-
pounds 4a–c were obtained through acylation of 2-(4-
aminophenyl)acetonitrile with benzoyl chlorides 3a–c.[5c]
Knoevenagel reaction between compounds 2 and 4a–c af-
Scanning electron microscopy (SEM) images of air-dried
forded the target molecules CN-DBAPPBn. The new com- gels were obtained to gain insight into the morphology of
pounds were characterized by 1H NMR, MALDI-TOF- the organogels of CN-DBAPPBn. As shown in Figure 1 (a–
MS, FTIR spectrometry, and elemental analysis.
d) and Figure S1a–b, the SEM images of air-dried gels
2
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C3-Symmetrical Cyano-Substituted Triphenylbenzenes
Table 1. Gelation ability of CN-DBAPPBn in organic solvents.[a]
meters could be observed in the 1,4-dioxane gel of CN-
DBAPPB3 (Figure 1, f and Figure S1d). The entangled fi-
brillar structures of the CN-DBAPPB3 in benzaldehyde
and CN-DBAPPB3 rods in 1,4-dioxane could be directly
observed from the air-dried gels by fluorescence microscopy
images under an epifluorescence microscope equipped with
330–385 nm excitation filter and a long-pass emission filter
(Ͼ420 nm; Figure 1, g and h). It is therefore clear that the
solvents have a clear effect on the morphology of the gel
materials. In addition, XRD data revealed poor long-dis-
tance ordering of CN-DBAPPBn in 1,2-dichlorobenzene
and toluene (Figure S3a) because no distinguishable peak
was observed in the low angle region. On the other hand,
the results suggested that a layered structure[10a–c] emerged
in the gel of CN-DBAPPB3 in benzaldehyde with a d-spac-
ing of 4.40 nm, and CN-DBAPPB3 packed into a one-
Solvent
CN-
DBAPPB1
CN-
DBAPPB2
CN-
DBAPPB3
Toluene
p-Xylene
Benzene
TG[b]
TG[b]
TG[b]
TG[b]
TG[c]
TG[d]
OG[d]
OG[b]
S
OG[c]
OG[c]
OG[c]
OG[c]
OG[d]
OG[d]
OG[d]
OG[b]
G[d]
OG[e]
S
OG[c]
OG[c]
OG[c]
OG[c]
OG[d]
OG[d]
OG[d]
OG[b]
S
1,2-Dichlorobenzene
Bromobenzene
Benzaldehyde
1,4-Dioxane
DMSO
Chloroform
Dichloromethane
DMF
OG[e]
S
UG
UG
Is
Ethanol
Is
Is
Methanol
n-Hexane
Is
Is
Is
S
Is
S
Cyclohexane
Tetrachloromethane
Acetonitrile
THF
Is
S
Is
S
S
S
Is
S
S
S
Is
S
dimensional columnar structure with
a diameter of
ca. 4.60 nm in 1,4-dioxane gel (Figure S3b).[10d,10e]
1
UV/Vis absorption, FTIR, and H NMR spectra were
[a] TG: transparent gel, OG: opaque gel, UG: unstable gel, S: solu-
ble at room temperature or when heated, Is: insoluble at room tem-
perature and when heated. [b] CGC = 0.5 wt./vol.-%. [c] CGC =
2.0 wt./vol.-%. [d] CGC = 5.0 wt./vol.-%. [e] CGC = 5.0 wt./vol.-
% below 15 °C or Ն 12.5 wt./vol.-% at room temperature.
recorded to investigate the driving forces behind the gela-
tion of CN-DBAPPBn. The UV/Vis absorption spectra of
CN-DBAPPBn in 1,2-dichlorobenzene and toluene are de-
picted in Figure 2 (a) and Figure S5a–b. As shown in Fig-
ure 2 (a), in dilute solutions, CN-DBAPPB1 gave absorp-
tion bands at 360 and 370 nm in toluene and in 1,2-di-
chlorobenzene, respectively, however, the absorption bands
clearly broadened in the gel states possibly due to π–π inter-
actions. In the case of CN-DBAPPB3, an absorption band
at 376 nm appeared in dilute solution in benzaldehyde, and
in the gel state the band broadened with a shoulder at ca.
440 nm (Figure 2, b), indicating that π–π interaction was a
driving force for the molecular aggregation in benzaldehyde
gel. On the other hand, no marked absorption spectral
change was detected for CN-DBAPPB3 in the 1,4-dioxane
gel phase by comparison to the dilute solution (Figure 2,
b). This illustrated that π–π interactions between the gelator
molecules had either no effect or only weak effects on gel
formation in 1,4-dioxane, which can be further confirmed
by the excitation spectra. From Figure 2 (c), it can be seen
that the excitation spectra of CN-DBAPPB3 showed similar
spectral development in solution and in the gel phase in
1,4-dioxane. The benzaldehyde gel of CN-DBAPPB3 gave
a broad excitation band in the range of 300–475 nm com-
pared with that in benzaldehyde solution, indicating the for-
mation of π-aggregates in benzaldehyde gel.
(xerogels) of CN-DBAPPBn obtained from 1,2-dichloro-
benzene and toluene showed heavily entangled amorphous
assemblies. The samples were then observed by visible-light
microscopy, whereby, as shown in Figure S2a–h, some orga-
nized structures could be identified. To be specific, fiber-
like network structures were formed in CN-DBAPPB3 gel
obtained from 1,2-dichlorobenzene (Figure S2e). Notably,
the organogels of CN-DBAPPB3 obtained from benzalde-
hyde created entangled, three-dimensional networks con-
sisting of both right- and left-handed helical fibers with
200–500 nm diameters and several tens of micrometers in
length; such large helical fibers were built up from thinner
fibers with diameters of 80–150 nm (Figure 1, e and Fig-
ure S1c). On the other hand, polygonal rods with diameters
of 2–15 μm and lengths varying from 5 μm to tens of micro-
The FTIR spectra of CN-DBAPPBn (Figure S4) reveal
that the amide I band of CN-DBAPPB1 appeared at 1649
and 1651 cm–1 in the xerogels obtained from toluene and
1,2-dichlorobenzene, respectively (Figure S4a).[8c,11] Simi-
larly, the amide I band in CN-DBAPPB2 emerged at
1655 cm–1 in both toluene and 1,2-dichlorobenzene xerogels
(Figure S4b), and that of CN-DBAPPB3 in the same sol-
vents appeared at 1665 cm–1 (Figure S4c). These observa-
tions indicate that the extent of intermolecular H-bonding
in the gels of CN-DBAPPBn was in order: CN-
Figure 1. SEM images of the dried gels obtained from (a) CN-
DBAPPB1, (b) CN-DBAPPB2, and (c) CN-DBAPPB3, obtained
in 1,2-dichlorobenzene (2.0 wt./vol.-%); CN-DBAPPB3 obtained
(d) in toluene, (e) in benzaldehyde, and (f) in 1,4-dioxane (2.0 wt./
vol.-%). Fluorescence microscopy images of the dried gels of CN-
DBAPPB3 obtained in (g) benzaldehyde (2.0 wt./vol.-%) and
(h) 1,4-dioxane (2.0 wt./vol.-%) under irradiation of 330–385 nm
light.
DBAPPB1ϾCN-DBAPPB2ϾCN-DBAPPB3.[12]
The
weak H-bonding in the case of CN-DBAPPB3 is possibly
due to the steric bulk of the alkyl chains, which prevent
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the core units from interacting. In addition, concentration-
1
dependent H NMR spectra were recorded to deduce the
extent of H-bonding in the gelation process. Figure 3 shows
the 1H NMR spectra of CN-DBAPPB2 in CDCl3 at
3.6ϫ10–3 and 7.2ϫ10–4 m. It is clear that the peak for the
protons in N–H resonates at δ = 7.90 ppm at low concentra-
tion, and is shifted downfield to 7.93 ppm at higher concen-
tration, illustrating the participation of H-bonding of the
amide in the formation of gels.
Figure 3. 1H NMR spectra of CN-DBAPPB2 in CDCl3 at
(i) 3.6ϫ10–3 m; (ii) 7.2ϫ10–4 m.
Aggregation-Induced Emission (AIE) in Gels
When illuminated with 365 nm light, the gels of CN-
DBAPPBn emitted, to some extent, blue or greenish-yellow
light with emission maxima ranging from 490 to 535 nm
(Figure 4 and Figure S6) depending on the solvent and gel-
ator used. For example, the benzaldehyde gel of CN-
DBAPPB3 emitted strong greenish-yellow light with an
emission centered at 520 nm (Figure S6a), whereas the gel
with 1,4-dioxane gave a greenish-blue light with an emission
located at 490 nm (Figure S6b) when illuminated with
365 nm light. Likewise, as can clearly be seen in Figure 1
(g–h), the entangled fibers obtained from the benzaldehyde
gel of CN-DBAPPB3 emit greenish-yellow light, whereas
the nanorods obtained from the 1,4-dioxane gel of CN-
DBAPPB3 give greenish-blue light when examined under
an epifluorescence microscope equipped with 330–385 nm
excitation filter and a long-pass emission filter (Ͼ420 nm).
Therefore, the microstructures of the self-assemblies of CN-
DBAPPBn in the gel phases have an effect on their fluores-
cence properties. The emission of CN-DBAPPB3 in benzal-
dehyde gel appeared at a lower energy region than that in
1,4-dioxane gel (Figure S6), suggesting that the π–π interac-
Figure 2. UV/Vis absorption spectra of (a) CN-DBAPPB1 in tolu-
ene (black solid line: dilute solution at 0.02 wt./vol.-%; black
dashed line: gel at 2.0 wt./vol.-%), and in 1,2-dichlorobenzene (gray
solid line: dilute solution at 0.02 wt./vol.-%; dashed gray line: gel
at 2.0 wt./vol.-%); (b) CN-DBAPPB3 in benzaldehyde (black solid
line: dilute solution at 0.02 wt./vol.-%; black dashed line: gel at 2.0 tions in benzaldehyde gel were stronger than those in 1,4-
wt./vol.-%), and in 1,4-dioxane (gray solid line: dilute solution at
dioxane, which is consistent with the UV/Vis absorption
0.02 wt./vol.-%; gray dashed line: gel at 2.0 wt./vol.-%). (c) Exci-
and excitation spectra.[4d] Furthermore, the concentration-
tation spectra of CN-DBAPPB3 in benzaldehyde (black solid line:
dependent fluorescence emission spectra of CN-DBAPPBn
dilute solution at 0.02 wt./vol.-%, λem = 462 nm; black dashed line:
and the fluorescence spectral changes observed during sol-
gel transitions in 1,2-dichlorobenzene and toluene were re-
corded. It was found that in 1,2-dichlorobenzene the emis-
gel at 2.0 wt./vol.-%, λem = 520 nm); and in 1,4-dioxane (solid gray
line: dilute solution at 0.02 wt./vol.-%, λem = 473 nm; gray dashed
line: gel at 2.0 wt./vol.-%, λem = 490 nm).
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C3-Symmetrical Cyano-Substituted Triphenylbenzenes
sion band of CN-DBAPPB1 in dilute solution (0.02 wt./ the emission intensity of CN-DBAPPB1 increased during
vol.-%) appeared at 477 nm, and redshifted to 532 nm in the sol-gel transition process, meaning the gelator showed
solution at a concentration of 2.0 wt./vol.-% (Figure 4, a AIE behavior. Similarly, CN-DBAPPB2 and CN-
and b). Upon the formation of a stable gel, the emission DBAPPB3 also exhibited concentration-induced redshift
band of CN-DBAPPB1 further redshifted to 535 nm. Simi- and AIE properties, which might be due to the formation of
larly, in toluene, the emission band of CN-DBAPPB1 red- J-aggregates, enhancement of coplanarization of the cyano-
shifted from 488 nm in dilute solution to 518 nm in concen- substituted π-conjugated triphenylbenzene core, and restric-
trated solution, and further shifted to 527 nm in the stable tion of motion.[13] Although similar fluorescence emission
gel phase. Such significant bathochromic shifts of CN- changes have been detected for CN-DBAPPB2 and CN-
DBAPPB1 from dilute solution to gel phase illustrated that DBAPPB3 (Figure 4, c–f), the emission intensities of the
π–π interactions were involved in gel formation. Notably, stable gels became lower with increasing number of alkyl
Figure 4. Fluorescence emission spectra (light gray, 0.02 wt./vol.-%; black, 2.0 wt./vol.-%; excited at 365 nm) of CN-DBAPPB1 (a) in 1,2-
dichlorobenzene, (b) in toluene; CN-DBAPPB2 (c) in 1,2-dichlorobenzene, (d) in toluene; CN-DBAPPB3 (e) in 1,2-dichlorobenzene, (f)
in toluene. The insets show the corresponding gel phases under daylight (left) and 365 nm irradiation (right).
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chains. The alkyl chains possibly prevent the π-cores from UV/Vis absorption spectral changes of CN-DBAPPBn in
coming closer together, thus weakening the π–π interac- THF and in THF/H2O were recorded (Figure 6, a, c, and
tions, which is consistent with the FTIR data.
e). In pure THF, only one absorption band for each CN-
DBAPPB1, CN-DBAPPB2, and CN-DBAPPB3 emerged
at 270, 270, and 265 nm, respectively, which was ascribed
to the electronic transition of isolated species in twisted
conformation and with reduced conjugated length. Upon
Aggregation-Induced Emission (AIE) in Nanoparticles
When water was injected into solutions of CN- addition of water into solutions of CN-DBAPPBn in THF,
DBAPPBn in THF, spherical or cubic organic nanopar- the peaks at ca. 270 nm redshifted and became less intense,
ticles were generated.[9c,14] From Figure S7, it can be seen meanwhile, new broad bands in the range of 360–411 nm
that the organic nanosuspensions based on CN-DBAPPBn appeared. For instance, the two absorption bands at 293
(4.6ϫ10–5 molL–1) in THF/water in capped-vials look and 375 nm were detected for CN-DBAPPB1 in THF/water
cloudy when the amount of the poorly miscible solvent (60%, 2:3 v/v), which suggested that π–π interactions played
(water) increased. We also found that the suspensions of a key role in the formation of the nanoparticles in which J-
nanoparticles could be maintained for at least two months aggregates were formed.[14b,14c]
without the formation of precipitates. This long-term sta-
bility is likely due to the negative ζ potential arising from
the polar groups (CN and CO), which has been observed
in organic nanoparticles in water.[14b] As shown in Figure 5,
SEM images show that spherical particles (CN-DBAPPB1
and CN-DBAPPB2) and/or cubic particles (CN-
DBAPPB3) were obtained in the mixture of THF/water (1:4
v/v). The diameters of the nanospheres varied from 40 to
410 nm for CN-DBAPPB1 and from 60 to 250 nm for CN-
DBAPPB2. In the case of CN-DBAPPB3, significantly
fewer spherical nanoparticles with diameters of about
160 nm were obtained, and many more cubic nanoparticles
with side-length in the range of 285–422 nm were found. It
is interesting that the fluorescence emission intensities of
the nanoparticle suspensions of CN-DBAPPBn were much
higher than those in pure THF. Such AIE phenomenon is
consistent with the results obtained from compounds in the
gel phases. The fluorescence spectral changes of CN-
DBAPPBn in THF/water with different amounts of water
(Figure 6, b, d, and f) clearly show that CN-DBAPPB1,
CN-DBAPPB2, and CN-DBAPPB3 gave very weak emis-
sion at 454, 450, and 444 nm, respectively, in pure THF.
When a small amount of water was added (10–20%), a
notable increase of emission intensity was observed either
accompanied or not by a redshift of the emission band rela-
tive to those in pure THF. When the amount of water was
increased to 80%, a notable redshift of the emission was
observed and the emission intensities increased rapidly. For
example, in THF/water with 30% water, the emission bands
of CN-DBAPPB1, CN-DBAPPB2, and CN-DBAPPB3
were located at 454, 482, and 455 nm, respectively, which
Figure 5. SEM images of the nanoparticles of (a) CN-DBAPPB1,
further redshifted to 485, 491, and 484 nm in THF/water
(b) CN-DBAPPB2, and (b) CN-DBAPPB3 obtained from THF/
water suspensions (80% water).
with 80% water. We concluded that π–π interactions oc-
curred in the formation of the nanoparticles, and that the
increase in AIE for CN-DBAPPBn in the nanosuspensions
in THF/water with higher amounts of water might be due
to coplanarization of the C3-backbones under strong π–π
interactions. In addition, the images of CN-DBAPPBn in
Conclusions
THF and in THF/H2O under 365 nm light illumination (in-
Three new C3-symmetrical discotic molecules consisting
sets in Figure 7) show that the nanosuspensions gave strong of a triphenylbenzene core linked to three N-phenylbenz-
fluorescence, whereas the isolated species in THF are al- amide groups by a cyano-substituted vinylene moiety were
most entirely nonfluorescent. To gain more information on synthesized. It was found that CN-DBAPPBn can self-as-
the origin of emission enhancement for nanosuspensions, semble in different solvents into organogels exhibiting
6
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Figure 6. UV/Vis absorption spectra of (a) CN-DBAPPB1, (c) CN-DBAPPB2, and (e) CN-DBAPPB3 in THF and THF/water. Fluores-
cence emission spectra of (b) CN-DBAPPB1, (d) CN-DBAPPB2, and (f) CN-DBAPPB3 in THF and THF/water (λex = 365 nm; concen-
tration was 4.6ϫ10–5 molL–1 in all samples).
architectures such as amorphous and fibrous assemblies, ticles based on CN-DBAPPBn in the mixture of THF/
patent helical fibers, and rods. The results of UV/Vis ab- water. Notably, AIE behavior was observed in gel phases
sorption, FTIR, 1H NMR, fluorescence excitation and and in nanoparticles. Therefore, the synthesized C3-sym-
emission measurements suggest that π–π interactions and metrical discotic π-conjugated molecules with controllable
H-bonding are responsible for the gelation of CN- fluorescence can be used as functional soft materials and
DBAPPBn. In addition, the reprecipitation method was be applied in sensors or optoelectronic devices and related
employed to generate spherical or cubic organic nanopar- fields.
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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O. Simalou, R. Lu, P. Xue, P. Gong, T. Zhang
FULL PAPER
1
solid, m.p. Ͼ200.0 °C. H NMR (500 MHz, CDCl3): δ = 7.69 (s, 3
H, Ar-H), 7.61 (d, 6 H, Ar-H), 7.53 (d, 6 H, Ar-H) ppm. FTIR
(KBr): ν = 3150, 1075, 1006, 809 (C–Br) cm–1. MALDI-TOF MS:
˜
m/z = 544.6 [M + H]+. C24H15Br3 (543.09): calcd. C 53.10, H 2.83;
found C 53.01, H 2.81.
1,3,5-Tris(4-formaldehydephenyl)benzene (2): nBuLi (2.88 m in n-
hexane, 9.6 mL, 5 equiv.) was added dropwise to an anhydrous
solution of tribromophenylbenzene 1 (3.0 g, 5.5 mmol) in THF
(120 mL) under N2 at –78 °C. When the addition of nBuLi was
complete, the temperature of the mixture was allowed to increase
to room temperature, and the mixture was stirred for another
30 min. The mixture was then cooled to –78 °C and anhydrous
DMF (2.6 mL, 33 mmol, 6 equiv.) was added dropwise. After stir-
ring for 24 h at room temperature, dilute HCl was added and the
yellow precipitate that appeared was collected by filtration. After
recrystallization from ethanol, 2 (1.38 g, 64%) was afforded as a
yellow solid, m.p. Ͼ200.0 °C. 1H NMR (500 MHz, CDCl3): δ =
10.14 (s, 3 H, CHO), 8.06 (d, 6 H, Ar-H), 7.94 (s, 3 H, Ar-H), 7.91
Figure 7. The emission maxima bathochromic shifts of CN-
DBAPPB1 (squares), CN-DBAPPB2 (circles), and CN-DBAPPB3
(triangles) in THF/water relative to those in THF. The insets show
the images of CN-DBAPPB1 (top-left), CN-DBAPPB2 (middle-
left), and CN-DBAPPB3 (bottom-right) in THF and THF/water
illuminated with 365 nm light. The concentration was
4.6ϫ10–5 molL–1 in all samples.
(d, 6 H, Ar-H) ppm. FTIR (KBr): ν = 2807 and 2720 (C–H of
˜
CHO), 1689 (C=O), 1603, 1213, 1171 cm–1. MALDI-TOF MS: m/z
= 389.0 [M + H]+. C27H18O3 (390.44): calcd. C 83.10, H 4.62;
found C 83.11, H 4.60.
2-[4-(4-Dodecyloxybenzoylamino)phenyl]-1-acetonitrile (4a): A solu-
tion of benzoyl chloride 3a (2.4 g, 7.42 mmol) in anhydrous THF
(5 mL) was added dropwise to a solution of 2-(4-aminophenyl)ace-
tonitrile (0.98 g, 7.42 mmol) and triethylamine (0.8 mL, 7.42 mmol)
in anhydrous THF (20 mL) at 0 °C. After stirring at room tempera-
ture for 24 h, the solution was poured into water (300 mL) and the
precipitate was filtered and purified by column chromatography
(silica; CH2Cl2/ethyl acetate, 12:1 v/v) to give 4a (2.03 g, 65%) as
an off-white solid, m.p. 157.0–160.0 °C. 1H NMR (500 MHz,
CDCl3): δ = 7.83 (d, 2 H, Ar-H), 7.74 (s, 1 H, N-H), 7.66 (d, 2 H,
Ar-H), 7.33 (d, 2 H, Ar-H), 6.97 (d, 2 H, Ar-H), 4.02 (t, 2 H,
CH2O), 3.74 (s, 2 H, CH2CN), 1.83 (m, 2 H, CH2), 1.46 (m, 2 H,
CH2), 1.27 (m, 16 H, CH2), 0.88 (t, 3 H, CH3) ppm. FTIR (KBr):
Experimental Section
General Information: Solvents were dried by using conventional
methods. All others materials were used as received. 1H NMR spec-
tra were recorded with a Mercury Plus 500 MHz using CDCl3 or
[D6]DMSO as solvents. Mass spectra were performed with an
Agilent 1100 MS series and an AXIMA CFR MALDI/TOF
(Matrix assisted laser desorption ionization/time-of-flight) MS
(COMPACT); anthracene-1,8,9-triol was used as matrix. Elemental
analyses were recorded with a Perkin–Elmer 240C elemental ana-
lyzer. UV/Vis absorption spectra were recorded with a Shimadzu
UV-1601PC spectrophotometer in a cell with 3 mm width (gel
phase samples were sandwiched between two glass plates). Fluores-
cence spectra were recorded with a Shimadzu RF-5301 lumines-
cence spectrometer. Fluorescence microscopy images were taken
with an Olympus Reflected Fluorescence System BX51 (Olympus,
Japan). FTIR spectra were measured with a Nicolet-360 FTIR
spectrometer by incorporating samples in KBr pellets. X-ray dif-
fraction (XRD) patterns were recorded with a Japan Rigaku D/
max-γA instrument. The XRD instrument used graphite mono-
chromatized Cu-Kα radiation (λ = 1.5418 Å), and a scanning rate
of 0.02 s–1 in the 2θ range from 0.7 to 10°. Scanning electron micro-
scopy (SEM) observations were carried out with a Japan Hitachi
model X-650 San electron microscope. The samples for these mea-
surements were prepared by casting the organogels or nanoparticle
suspensions on silicon wafers and drying at room temperature, and
then coating with gold.
ν = 3372 (N–H), 2916, 2849, 2247 (–CN), 1649 (C=O) cm–1.
˜
MALDI-TOF MS: m/z = 421.75 [M + H]+. C27H36N2O2 (420.59):
calcd. C 77.10, H 8.62, N 6.71; found C 77.06, H 8.59, N 6.70.
2-[4-(3,5-Didodecyloxybenzoylamino)phenyl]-1-acetonitrile
(4b):
Synthesized by a similar procedure to that used for 4a. CH2Cl2 was
used as eluent for column chromatography (silica), yield 60%, m.p.
72.0–75.0 °C. 1H NMR (500 MHz, CDCl3): δ = 7.76 (s, 1 H, N-
H), 7.66 (d, 2 H, Ar-H), 7.33 (d, 2 H, Ar-H), 6.95 (s, 2 H, Ar-H),
6.62 (s, 1 H, Ar-H), 3.99 (t, 4 H, CH2O), 3.75 (s, 2 H, CH2CN),
1.79 (m, 4 H, CH2), 1.45 (m, 4 H, CH2), 1.27 (m, 32 H, CH2), 0.88
(t, 6 H, CH ) ppm. FTIR (KBr): ν = 3357 (N–H), 2920, 2852, 2250
˜
3
(–CN), 1654 (CO) cm–1. MALDI-TOF MS: m/z
= 606.7
[M + H]+. C39H60N2O3 (604.91): calcd. C 77.40, H 10.0, N 4.62;
found C 77.36, H 9.98, N 4.60.
2-[4-(3,4,5-Tridodecyloxybenzoylamino)phenyl]-1-acetonitrile (4c):
Synthesized by a similar procedure to that used for 4a. CH2Cl2 was
used as eluent for column chromatography, yield 75%, m.p. 89.0–
92.0 °C. 1H NMR (500 MHz, CDCl3): δ = 7.75 (s, 1 H, N-H), 7.69
(d, 2 H, Ar-H), 7.36 (d, 2 H, Ar-H), 7.20 (s, 2 H, Ar-H), 4.07 (t, 6
H, CH2O), 3.77 (s, 2 H, CH2CN), 1.82 (m, 6 H, CH2), 1.51 (m, 6
H, CH2), 1.29 (m, 48 H, CH2), 0.90 (t, 9 H, CH3) ppm. FTIR
Synthesis: Alkoxybenzoyl chlorides 3a–c were synthesized accord-
ing to a general procedure and used without any further purifica-
tion.[5c] Unless otherwise noted, all materials were obtained from
commercial suppliers and used without further purification.
1,3,5-Tris(4-bromophenyl)benzene (1): SiCl4 (25 mL, 0.225 mol) was
added dropwise to a solution of p-bromoacetophenone (10 g,
50 mmol) in absolute ethanol (80 mL) at 0 °C. A red mixture was
formed immediately. The mixture was heated to reflux for 24 h,
during which the mixture became yellow. After cooling to room
temperature, saturated NH4Cl (100 mL) was added and the mixture
was stirred for 30 min. The obtained precipitate was filtered and
recrystallized from ethanol to give 1 (7.9 g, 87%) as a pale-white
(KBr): ν = 3375 (N–H), 2917, 2850, 2248 (–CN), 1660 (C=O) cm–1.
˜
MALDI-TOF MS: m/z = 789.3 [M + H]+. C51H84N2O4 (789.24):
calcd. C 77.60, H 10.70, N 3.50; found C 77.54, H 10.65, N 3.50.
1,3,5-Tri{2-cyano-2-[4-(4-dodecyloxybenzoylamino)phenyl]-1-
ethenyl}phenylbenzene (CN-DBAPPB1): Nitrile 4a (0.39 g,
0.92 mmol), trialdehyde 2 (0.12 g, 0.30 mmol), and a catalytic
8
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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C3-Symmetrical Cyano-Substituted Triphenylbenzenes
amount of NaOH (25 mg) were dissolved in a mixture ethanol/
THF (1:5 v/v, 25 mL) and the solution was gently heated to reflux
for 12 h. After cooling to room temperature, the mixture was
poured into water (500 mL) and the solid was collected by fil-
tration. After purification by column chromatography (silica;
CH2Cl2/THF, 25:1 v/v), CN-DBAPPB1 (0.26 g, 55%) was obtained
as a yellow solid, m.p.Ͼ 200 °C. 1H NMR (500 MHz, CDCl3): δ
= 8.19 (d, 6 H, Ar-H), 8.11 (m, 12 H, Ar-H and N-H), 7.98 (t, 15
H, Ar-H and vinyl-H), 7.81 (d, 6 H, Ar-H), 7.06 (d, 6 H, Ar-H),
4.06 (t, 6 H, CH2O), 1.74 (m, 6 H, CH2), 1.43 (m, 6 H, CH2), 1.25
Acknowledgments
Support from the National Natural Science Foundation of China
(NSFC) (grant numbers 51073068, 21374041 and 20901081), Open
Project of State Key Laboratory of Supramolecular Structure and
Materials (SKLSSM201407), Postdoctoral Program for African
Researchers of China-Africa Science and Technology Partnership
Program (CASTEP).
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1922–1932.
(m, 48 H, CH ), 0.86 (t, 9 H, CH ) ppm. FTIR (KBr): ν = 3404
˜
2
3
(N–H), 2922, 2852, 2213 (–CN), 1651 (C=O), 1605, 1515, 1405,
1244 cm– 1 . MALDI-TOF MS: m/z = 1598.2 [M + H]+
108H120N6O6 (1598.17): calcd. C 81.20, H 7.61, N 5.32; found C
80.98, H 7.60, N 5.29.
.
C
1,3,5-Tri{2-cyano-2-[4-(3,5-didodecyloxybenzoylamino)phenyl]-1-
ethenyl}phenylbenzene (CN-DBAPPB2): Synthesized by a similar
procedure to that used for CN-DBAPPB1. CH2Cl2 was used as
eluent for column chromatography, yield 49 %, m.p. 115.5–
117.5 °C. 1H NMR (500 MHz, CDCl3): δ = 8.04 (d, 6 H, Ar-H),
7.91 (s, 3 H, N-H), 7.87 (s, 3 H, Ar-H), 7.82 (d, 6 H, Ar-H), 7.75
(d, 12 H, Ar-H), 7.60 (s, 3 H, vinyl-H), 6.98 (s, 6 H, Ar-H), 6.63
(s, 3 H, Ar-H), 4.01 (t, 12 H, CH2O), 1.79 (m, 12 H, CH2), 1.47
(m, 12 H, CH2), 1.27 (m, 96 H, CH2), 0.88 (t, 18 H, CH3) ppm.
FTIR (KBr): ν = 3374 (N–H), 2924, 2852, 2213 (–CN), 1653
˜
(C=O), 1593, 1520, 1401, 1242, 1160 cm–1. MALDI-TOF MS: m/z
= 2150.9 [M + H]+. C144H192N6O9 (2151.14): calcd. C 80.40, H
9.00, N 3.90; found C 80.72, H 8.96, N 3.87.
1,3,5-Tri{2-cyano-2-[4-(3,4,5-tridodecyloxybenzoylamino)phenyl]-1-
ethenyl}phenylbenzene (CN-DBAPPB3): Synthesized by a similar
procedure to that used for CN-DBAPPB1. CH2Cl2 was used as
eluent for column chromatography, yield 54 %, m.p. 135.0–
138.0 °C. 1H NMR (500 MHz, CDCl3): δ = 8.06 (s, 6 H, Ar-H),
7.91 (s, 3 H, N-H), 7.84 (d, 6 H, Ar-H), 7.78 (s, 3 H, Ar-H), 7.76
(d, 6 H, Ar-H), 7.74 (d, 6 H, Ar-H), 7.60 (d, 3 H, vinyl-H), 7.09
(s, 6 H, Ar-H), 4.04 (m, 18 H, CH2O), 1.82 (m, 18 H, CH2), 1.48
(m, 18 H, CH2), 1.27 (m, 144 H, CH2), 0.88 (t, 27 H, CH3) ppm.
FTIR (KBr): ν = 3377 (N–H), 2924, 2852, 2214 (–CN), 1659
˜
(C=O), 1596, 1519, 1466, 1399, 1105 cm–1. MALDI-TOF MS: m/z
calcd. [M + H]+ 2704.36; found 2724.2. C180H264N6O12 (2704.10):
calcd. C 80.00, H 9.80, N 3.10; found C 79.96, H 9.84, N 3.11.
Preparation of Organogels: A weighed amount of the compound
was added to a sealable glass vial with an appropriate solvent. The
vial was sealed and the mixture was heated until the compound
was dissolved. The solution was cooled to room temperature and
gel formation was confirmed by inverting the glass vial. The revers-
ibility of the sol-gel transition was performed by repeated heating
and cooling. The critical gelator concentration (CGC) was deter-
mined from the minimum amount of gelator required for the for-
mation of gel at room temperature.
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460; Angew. Chem. 2006, 118, 470; c) G. Bastiat, J.-C. Leroux,
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Preparation of Nanosuspensions: Upon injected of water into solu-
tions of CN-DBAPPBn in THF, nanoparticle suspensions were ob-
tained; the concentrations were maintained at 4.6ϫ10–5 molL–1 in
all samples.
Supporting Information (see footnote on the first page of this arti-
cle): SEM images, visible-light microscopy images, XRD patterns
of CN-DBAPPBn, FTIR spectra of the xerogels of CN-DBAPPBn
and the solid of CN-DBAPPB3, UV/Vis spectra of CN-DBAPPB2
and CN-DBAPPB3 in 1,2-dichlorobenzene and toluene, Sol-gel
fluorescence emission spectra of CN-DBAPPB3 in benzaldehyde
and 1,4-dioxane, nanoparticle suspension images, 1H NMR and
MALDI/TOF MS spectra of all synthesized compounds.
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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O. Simalou, R. Lu, P. Xue, P. Gong, T. Zhang
FULL PAPER
L. Leiserrowitz, L. Addadi, S. Weiner, A. D. Hamilton, Adv.
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10
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Pages: 11
C3-Symmetrical Cyano-Substituted Triphenylbenzenes
Organogels
Three synthesized fluorescent organic
molecules based on tris{2-cyano-2-[4-(do-
decyloxybenzoylamino)phenyl]-1-ethenyl}-
phenylbenzene (CN-DBAPPBn, n = 1, 2,
3) were used to prepare organogel phases
in several organic solvents, and organic
nanoparticles in a mixture of THF and
water. Interestingly, both phases exhibit
aggregation-induced emission features.
O. Simalou, R. Lu,* P. Xue, P. Gong,
T. Zhang* ....................................... 1–11
C3-Symmetrical Cyano-Substituted Tri-
phenylbenzenes for Organogels and Or-
ganic Nanoparticles with Controllable
Fluorescence and Aggregation-Induced
Emission
Keywords: Aggregation / Colloids / Gels /
Nanoparticles / Fluorescence
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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11