Benzene Triimides: Facile Synthesis and Self-Assembly Study

Article abstract of DOI:10.1002/cjoc.201900146

Herein, we report an efficient one-pot condensation of maleimide derivatives in the presence of acetic acid and water to afford a series of benzene triimides (BTIs). The structure, physicochemical properties and electrochemistry behavior of BTIs were studied by means of X-ray crystallography, UV-Vis spectra, cyclic voltammetry and differential pulse voltammetry. Owing to the planar structure and unique electron-deficient nature, BTIs can self-assemble into different motifs including nanorod, nanotube, nanobrick and cross-linked structure depending on different N-substituents. The origin for different self-assemblies was ascribed to the intermolecular lone pair-π interaction or a balance of lone pair-π and π-π stacking.

Full text of DOI:10.1002/cjoc.201900146

Accepted Article
Title: Benzene Triimides (BTIs): Facile Synthesis and Self-Assembly Study
Authors: De-Hui Tuo, Qing He, Qi-Qiang Wang,* Yu-Fei Ao, and De-Xian Wang*
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Benzene Triimides (BTIs): Facile Synthesis and Self-Assembly Study
De-Hui Tuo,+[a,b] Qing He,+[a] Qi-Qiang Wang,*[a,b] Yu-Fei Ao,[a] and De-Xian Wang*[a,b]
a Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy
of Sciences, Beijing, 100190, China
b University of Chinese Academy of Sciences, Beijing 100049, China
+These two authors contribute equally
Cite this paper: Chin. J. Chem. 2019, 37, XXX—XXX. DOI: 10.1002/cjoc.201900XXX
Summary of main observation and conclusion Herein we report an efficient one-pot condensation of maleimide derivatives in the presence of acetic acid
and water to afford a series of benzene triimides (BTIs). The structure, physicochemical properties and electrochemistry behavior of BTIs were studied by
means of X-ray crystallography, UV-Vis spectra, cyclic voltammetry and differential pulse voltammetry. Owing to the planar structure and unique
electron-deficient nature, BTIs can self-assemble into different motifs including nanorod, nanotube, nanobrick and cross-linked structure depending on
different N-substituents. The origin for different self-assemblies was ascribed to the intermolecular lone pair-π interaction or a balance of lone pair-π and
π-π stacking.
methanol, but trimerize into BTI 2c in a high yield upon
elimination of three molecules of methylamine if aqueous
Background and Originality Content
Arylenediimides such as naphthalenediimide (NDI) and
methanol was used. Inspired by this “side reaction”, we set out to
perylenediimide (PDI) are among the fascinating class of
synthesize BTIs by developing this trimerization type reaction.
functional molecules that have been extensively applied in
electronics,[1] sensor,[2] self-assembly[3] and catalysis.[4] In sharp
R
contrast, benzene triimide (BTI, Figure 1),[5]
a
planar
N
electron-deficient π unit possessing C3-symmetry has been largely
unexplored. Despite of their intriguing structure, high π-acidity
(Qzz = 14.5 B), good stability and facile functionalization features,
there are only a few reports on that BTIs can act as a
three-electron acceptor[5a] and can be used to fabricate extended
donor-acceptor column assemblies.[6] Besides, very limited
reports[7] have been made on BTI-related applications so far,
probably due to the synthetic difficulties. We envisioned that the
planar and π-acidic features of BTI unit endow it a good model in
electronics and supramolecular chemistry, particular for studying
self-assembly and anion-π interactions.[8] Reported herein are the
easy synthesis, the systematical investigation of their
physicochemical properties, and self-assembly behaviors of BTIs.
O
O
O
O
N
N
R
R
O
O
Figure 1. Structure and electrostatic potential (ESP) surface of BTI. The ESP
values were calculated at the isovalue of 0.001 eÅ-3 at the level of
MP2/aug-cc-pVDZ.[10]
The reaction conditions were firstly optimized by using
1-benzyl-3-benzylaminopyrrole-2,5-dione (1a) as
a
model
substrate. As listed in Table 1, reaction of 1a in CH3OH/H2O (v/v,
4:1) in the presence of HCl under either ambient or elevated
temperature only gave trace amounts of product 2a (<3% yield,
entries 1 and 2). Applying pyridinium 4-toluenesulfonate (PPTS) in
CH3OH/CHCl3 (1:1) or the use of acetic acid as pure solvent can
improve the yield to about 17% (entries 3 and 4). Pleasantly, using
a mixture of acetic acid and water (4:1) as solvent led to a yield of
66% (entry 6). It is worth noting that after reaction the major
product 2a precipitated from the solution and can be obtained by
simple filtration. Under the optimized condition, other maleimide
substrates 1b-1j were subjected and to our delight most reactions
proceeded smoothly and afforded versatile BTI derivatives in
moderate to good yields (Table 2). For the propargyl substituted
compound 2k, the trimerization strategy didn’t work and it was
Results and Discussion
Surprisingly, only several reports on the synthesis of BTIs can
be found in the literature.[5,9] In 2008 Hamilton et al. reported an
improved procedure[5b] on their original synthesis[5a] of BTIs in
acceptable yields (22%-55%) through heating the solid ammonium
salts formed between mellitic acid and 3 equiv. of primary amines.
The success required long-time heating at a high temperature
(140 °C, 96 h) and generally lengthy chromatography to remove
the unwanted byproducts. Meanwhile, an interesting reaction
reported by Chepyshev and coworkers has drawn our attention.[9d]
Therein 1-methyl-3-methylaminopyrrole-2,5-dione (1c) was found
to mainly dimerize in the presence of dry HCl in absolute
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Benzene triimides (BTIs): Facile Synthesis and Self-Assembly Study
Chin. J. Chem.
R1
alternatively synthesized through post N-functionalization of 2b
O
R2
N
N
with
propargyl
bromide
in
the
presence
of
O
O
O
O
R3
N,N-diisopropylethylamine (DIPEA) as a base (Scheme 1). The
proposed pathways for the condensation are summarized in
Scheme 2.
AcOH/H O
(v/v, 4/1)
2
R1
R1
N
N
reflux
O
O
N
1
O
R1
To understand the physicochemical properties of BTIs,
we took 2a, 2c and 2f as typical examples to investigate
their UV-Vis spectra and electrochemistry behavior. The
three compounds gave similar UV-Vis spectra in CHCl3
2
Entry Reactant
R1
R2
R3
Time
Yield of 2
1
2
3
4
5
1b
1c
1d
1e
1f
H
Me
H
Me
Me
Me
Me
Pr
3 h
3 h
3 h
3 h
3 h
2b 60%
2c 44%
2d 34%
2e 37%
2f 45%
Me
Et
Me
Me
H
i-Pr
n-Pr
(Figure 2A). The strong shoulder absorption band at λmax
= 266 – 302 nm (εmax = 104 M-1 cm-1) and the weak
absorption band at λmax = 320-340 nm can be ascribed to
the π-π* transition of the conjugated aromatic moiety
and the n-π* transition, respectively. The increased
absorption intensity of 2a than 2c and 2f is a result of
hyperchromic effect of the benzyl substituents. Table 1
Synthesis of 2a
6
7
8
9
1g
1h
1i
Me
Me
Me
Me
Me
Me
Me
Me
3 h
3 h
3 h
3 h
2g 63%
2h 57%
2i 9%
Br
Me
O
O
1j
2j 57%
11
Scheme 1 Synthesis of 2k
H
N
N
O
O
O
O
N
Bn
O
O
O
Br
O
O
N
O
H
O
DI
DMF
PEA,
HN
NH
N
N
O
O
24 h
rt,
Bn
Conditions
N
Bn
O
O
Bn
N
O
31%
O
2b
2k
O
O
N
O
Bn
2a
1a
Scheme 2 Proposed mechanism for the condensation reaction
Entry
Solvent
Acid Temperature Time Yield of 2a
1
2
3
4
5
6
CH3OH/H2O(v/v, 4:1)
CH3OH/H2O(v/v, 4:1)
HCl
HCl
reflux
rt
1 h
4 h
trace
<3%
CH3OH/CHCl3(v/v, 1:1) PPTS
reflux
reflux
reflux
reflux
6 h
<18%
17%
AcOH
AcOH
-
HCl
-
24 h
1 h
trace
66%
AcOH/H2O(v/v, 4:1)
3 h
Table 2 Synthesis of 2b-2j
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Wang et al.
NMe2
O
AcO-
O
2c
274
280
1.05
1.33
3.48
3.35
-1.04
-1.03
-4.06
-4.06
-7.54
-7.41
R
H
OH
N
O
O
N
Me2
N
N
AcO-
Me2
N
Me2
N
B
A
AcOH
2f
R
N
R
HO
N
R
N R
aEg = 1240/λabs
.
bHalf-wave reduction potentials obtained by DPV
opt
onset
R
1Me2
NMe2
O
O
O
O
AcO-
c
onset
NMe2R1
B
A
with ferrocene as the internal standard. LUMO = - (Ered
+EFc+/Fc + 4.8
eV). dHOMO = LUMO - Eg
.
opt
O
R
O
O
NMe2
NMe2
R
R
N
O
N
N
N
O
O
O
Me2
O
O
Me2
O
O
Me2
O
B
R
N
R
N R
N
To probe the molecular structure and intermolecular
interaction of 2, single crystals were cultivated. Pleasantly, single
crystals of 2a, 2f, 2g, 2i and 2k suitable for X-ray analyses were
obtained. As illustrated in Figures 3-4 and Figures S1-S3, all the BTI
backbones show nearly planar structure. The BTIs interact to each
other through lone pair-π interactions between the carbonyl
oxygens and the aromatic planes. Due to intrinsic direction of lone
pair-π interactions, two noncovalently bonded BTIs array with a
certain dihedral angle rather than in a parallel mode. The dihedral
angles change in the range of 66.2° to 80.3°, depending on the
substituents attached. Besides, the substituents show different
degrees of participation in the intermolecular interactions. For
example, the short alkyl, alkynyl, or amino acid moieties in 2f, 2i
and 2k do not significantly involve in the intermolecular
interactions (Figure 3 and Figure S2-S3). On the contrary, the
electronic rich aromatic substituents in 2a and 2g form π-π
stacking with the electron-deficient BTI core (Figure 4 and Figure
S1). Such different interaction details lead to different types of
packing motifs in solid state. In 2f, 2i and 2k, a three or
four-molecule entity noncovalently bonded by lone pair-π
interactions can be recognized as repeating unit. Extending of the
repeat unit produces a two-dimensional grid-like structure (Figure
3B). In the case of 2a and 2g, two neighboring BTI molecules form
a J-aggregated unit through lone pair-π interactions and π-π
stacking, from which a one-dimensional ladder-like structure is
formed (Figure 4A). The ladders are further connected through
π-π stacking to produce two-dimensional brick-like structure
(Figure 4B).
N
N
NMe2
NMe2
NMe2
O
O
O-
NMe2R1
N
N
N
N
NMe2R1
AcO-
NMe2R1
R
OH
R
OH
R
R
OH
O
AcO-
OH
O
R
R
N
O-
O
O
N
O
Me2
HO
O
O
N
R
NMe2
N
R
N R
NMe2
O
NMe2
N
Me2
N
Me2
N
O
O
O
O
O
N
N
N
NMe2R1
R
R
R
O
O
AcO-
R
N
O
O
O
O
O
=
R1
N
R
NR
RN
O
O
O
The redox properties of 2a, 2c and 2f were examined by means
of cyclic voltammetry (CV) and differential pulse voltammetry
(DPV). As depicted in Figure 2B and Figures S8 and S9, the CVs
showed three reversible redox couples corresponding to three
sequential and separated one-electron reductions (Figure S10).[5a]
It appeared that the half-wave reduction potentials (E1/2) as
obtained by means of DPV are hardly affected by the different
alkyl substituents, for example 2c and 2f gave almost identical E1/2
values (Figures S9). Replacing the alkyl group with benzyl group
lowered the first reduction potential (E1) by about 0.10 V.
Estimated from the absorption spectra and the reduction
potentials measured by DPV, the HOMO and LUMO energies were
determined and summarized in Table 3. For purpose of
comparison, we also measured the CV of di(n-butyl)-substituted
NDI (Figures S11 and S12). Notably, 2f showed comparable first
reduction potential as that of NDI (-1.03 V vs -0.94 V), indicating
BTI is nearly as electron-deficient as NDI.
Figure 3. Crystal structure of 2f. (A) a four-molecule entity noncovalently
bonded by lone pair-π interactions, (B) extended packing mode.
Figure 2. (A) UV-Vis spectra of 2a, 2c, 2f in CHCl3 at 298 K (8×10-5 M), and
(B) cyclic voltamograms of 2a, 2c, 2f (normalized at the internal standard
Fc+/Fc). CV measurements were carried out in dichloromethane containing
n-Bu4NPF6 (0.1 M). The potential scan rate is 100 mV/s.
Table 3 Summary of Physicochemical Properties of BTIs 2a, 2c and 2f
ε(×104
mol-1 cm-1)
Eg
E1
(V)b
LUMO
(eV)c
HOMO
(eV)d
opt
λmax
(nm)
(eV)a
2a
277
1.50
3.25
-1.12
-4.12
-7.37
Chin. J. Chem. 2019, 37, XXX－XXX
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Benzene triimides (BTIs): Facile Synthesis and Self-Assembly Study
Chin. J. Chem.
Figure 4. Crystal structure of 2a. (A) J-aggregated unit through lone pair-π
interactions and π-π stacking, (B) extended packing mode.
BTIs was also tested (Figures S24-31, in DMF). Interestingly, these
BTIs gave different types of self-assemblies. Typically, 2c, 2e and 2i
bearing
non-aromatic
substituents
produced
nanorod
Encouraged by the crystal structures and intermolecular
interactions, the self-assembly behavior of these BTI derivatives
was systematically studied. 2f was firstly taken to investigate the
self-assembly conditions including varied concentrations and
solvents. It was found that 2f formed hexagonal nanotubes in
acetonitrile with the concentration over 3×10-4 M, and only
irregular morphology could be observed when the concentration
was as low as 1×10-4 M (Figure S13). Hence, the three
concentrations of 4, 6, and 8×10-4 M were chosen and the effects
of various solvents, including CHCl3, THF, acetone, DMF, alcohol
solvents, water, and acetonitrile/water mixtures, were
investigated. In all cases, self-assembly formation was observed
and solvent-dependent assembled structures were obtained.
Generally, nanotube was formed in acetone, DMF and
acetonitrile/water mixtures, and the formation of nanorod was
facilitated in CHCl3, while both nanorod and nanotube-like
structures were observed in THF (Figure 5 and Figures S14-S17,
S23). Moreover, different morphologies were found in various
alcohol solvents, such as co-existence of nanoparticle and gel-like
morphology in ethanol, nanorod in isopropanol, angular rod in
isobutanol and semi-nanotube in isopentanol, indicating the
significant effect of alcohol solvents (Figures S18-S21). It was
worth addressing that self-assembly of 2f in water could produce
thread and nanorod structures, with lower concentration favored
the formation of nanorod (Figure S22). The formation of nanotube
and nanorod self-assembly could be rationalized from crystal
packing (vide supra). The two-dimensional extending of the
four-molecule repeating unit can produce hexagonal and
triangular plates respectively, and their vertical aggregation could
produce corresponding hexagonal or triangular nanorods (Figure
5A and 5C). The formation of hexagonal nanotube could be due to
the local fast evaporation of solvent which caused defect inside
the nanorod (Figure 5B and 5D).
self-assemblies, with the morphology of nanorod affected by
steric hindrance of the substituents. While methyl (2c) produced
similar nanorod as n-Pr (2f), the increased substituent bulkiness in
2e and 2i led to loosened or short nanorods. In contrast, the
aryl-substituted BTIs behaved differently (Figure 6). For example,
the benzyl substituted BTI 2a produced highly ordered nanobrick
morphology. Such dramatic structural change could be caused by
the intermolecular π-π stacking in the J-aggregation (Figure 4). In
case of 3-bromobenzyl (2g), thin thread morphology was
observed whereas no ordered self-assembly was found for
3-methylphenyl (2h). This could be reasonable as the increased
bulkiness in these two BTIs inhibit the efficient intermolecular π-π
stacking. The regulation effect of the substituents was further
highlighted by 2j where cross-linked morphology was formed
owing to the greatly enhanced hydrophobic effect of the long alkyl
substituents. Strangely, the propargyl substituted BTI 2k did not
show ordered self-assembly. In brief summary, with “weak” side
chains, the self-assembly was mainly dominated by the
interactions between the BTI cores (lone pair-π) and produced
nanorods or nanotubes. “Strong” substituents, however, could
bring additional intermolecular interaction (π-π stacking or
hydrophobic effect) and result in a change from nanorod to
nanobrick or cross-linked morphology as driven by a balance of
different noncovalent interactions. To obtain
a
further
understanding on the self-assembly mechanism, the solid-state
UV-Vis spectra of self-assembled samples of 2a and 2f were
recorded. The new but weak peaks emerged at around 400-460
nm probably imply intermolecular stacking after self-assembling
(Figure S4). Moreover, in the concentration-variable 1H NMR
spectra of 2f, the chemical shifts of the alkyl proton signals
remained unchanged within the varied concnetrations (1-80 mM),
in consistence with that the propyl substituent is less likely to
participate in the self-assembly (Figure S33). In case of 2a, the
benzyl proton signals show slightly upfield shifts upon
concentration increasing, indicating intermolecular π-π stacking
probably occur (Figure S32).
Figure 6. SEM images of the self-assembly of (A) 2a, (B) 2g and (C) 2h in
DMF (6×10-4 M).
Conclusions
In conclusion, a facile and efficient strategy for synthesis of
benzene triimides (BTIs) has been developed. The
electron-deficient nature, unique backbone structure, good
stability and facile functionalization ensure BTIs as useful building
blocks in self-assembly. The self-assembly structures can be not
only governed by the interactions between BTI cores but also
regulated by the side substituents, affording an enriched diversity.
Furthermore, due to its highly electron-deficiency, BTI could be
Figure 5. Self-assembly of 2f in THF (8×10-4 M). SEM images of (A) nanorod
and (B) nanotube-like structures, and (C, D) their corresponding possible
cross sections illustrated by the packing motif in crystal.
Based on the above results, the self-assembly behavior of other
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Wang et al.
versatile anion-π receptors. With the demonstration of convenient
synthesis and superior properties, we believe BTIs will find wide
applications on fabrication of functional architectures and
materials. Related studies are undergoing in this lab.
Found: 789.8790. Single crystal was obtained by slow diffusion of
acetonitrile into a solution of 2g in a mixture of nitromethane,
1,4-dioxane and DMF.
1
2h (yellow solid, 2.55 g, 57%): mp >300 °C; H NMR (400 MHz,
CDCl3, ppm): δ 7.44 (t, J = 6.4 Hz, 3H), 7.31-7.28 (m, 9H), 2.44 (s,
9H); 13C NMR (125 MHz, DMSO-d6, ppm): δ 161.9, 138.4, 133.1,
131.3, 129.3, 128.8, 127.8, 124.5, 20.8; IR (KBr) ν: 1778, 1730,
1657, 1632, 1490 cm-1; HRMS (APCI): m/z calcd: 556.1509 [M+H]+;
Found: 556.1502.
Experimental
General produce for synthesis of 2a-2j (taking 2a as a typical
example): Using the optimized reaction condition, the solution of
1a (5.12 g, 17.5 mmol) in a mixture of acetic acid and water (50
mL, 4/1, v/v) was heated at reflux for 3 h. Then the reaction
mixture was cooled to room temperature. The precipitate was
collected by filtration and washed with large amounts of acetic
acid and acetonitrile respectively to afford the pure product. For
products (2d-2g, 2i, 2j) not precipitated out from the reaction
mixture, the solvent was removed under vacuum and the residue
was chromatographed on a silica gel column (100-200 mesh) with
an elution (see belows).
2i (eluted with a mixture of petroleum ether and ethyl acetate.
White solid, 32 mg, 9%): mp 280-281 oC; 1H NMR (500 MHz, CDCl3,
ppm): δ 4.71 (d, J = 8.0 Hz, 3H), 3.73 (s, 9H), 2.86-2.79 (m, 3H),
1.20 (d, J = 6.5 Hz, 9H), 0.94 (d, J = 6.5 Hz, 9H); 13C NMR (125 MHz,
CDCl3, ppm): δ 168.3, 161.9, 133.6, 58.9, 53.0, 28.6, 21.3, 19.8; IR
(KBr) ν: 1780, 1734, 1367 cm-1; HRMS (ESI): m/z calcd: 628.2142
[M+H]+; Found: 628.2137. Single crystal was obtained by slow
diffusion of isopropyl ether into a solution of 2i in acetonitrile.
2j (eluted with a mixture of petroleum ether and ethyl acetate.
2a (white solid, 2.13 g, yield 66%): mp 286-287 °C; 1H NMR (400
MHz, DMSO-d6, ppm): δ 7.35-7.27 (m, 15H), 4.84 (s, 6H); 13C NMR
(100 MHz, DMSO-d6, ppm): δ 162.6, 135.9, 132.8, 128.5, 127.7,
127.6, 41.6; IR (KBr) ν: 1779, 1732, 1638, 1381 cm-1; HRMS (ESI):
m/z calcd: 556.1503 [M+H]+; Found: 556.1494. Single crystal was
obtained by slow diffusion of diethyl ether into a solution of 2a in
DCM.
1
White solid, 498 mg, 57 %): mp 91-92 °C; H NMR (300 MHz,
CDCl3, ppm): δ 3.81 (t, J = 6.8, 6H), 1.72 (br, 6H), 1.31-1.25 (m,
66H), 0.88 (t, J = 6.0, 9H); 13C NMR (125 MHz, CDCl3, ppm): δ
162.7, 133.5, 39.5, 32.1, 29.82, 29.79, 29.75, 29.70, 29.55, 29.49,
29.26, 28.3, 27.0, 22.8, 14.3; IR (KBr) ν: 1776, 1729, 1637, 1361
cm-1; HRMS (APCI): m/z calcd: 874.6673 [M+H]+; Found: 874.6649.
Synthesis of 2k: To a solution of 2b (285 mg, 1.0 mmol) and
propargyl bromide (428 mg, 3.6 mmol) in DMF (10 mL) was
added DIPEA (1 mL, 6.0 mmol). The resulting mixture was stirred
at room temperature for 24 h. After removal of solvent under
vacuum, the residue was chromatographed on a silica gel column
(100-200 mesh) with a mixture of DCM and acetone to give pure
1
2b (white solid, 183 mg, 60%): mp >300 °C; H NMR (400 MHz,
DMSO-d6, ppm): δ 12.06 (s, 3H); 13C NMR (125 MHz, DMSO-d6,
ppm): δ 164.1, 134.2; IR (KBr) ν: 3283, 1797, 1717, 1327 cm-1;
HRMS (ESI): m/z calcd: 283.9944 [M-H]-; Found: 283.9944.
1
2c (white solid, 240 mg, 44%): mp >300 °C; H NMR (300 MHz,
DMSO-d6, ppm): δ 3.12 (s, 9H); 13C NMR (75 MHz, DMSO-d6, ppm):
δ 163.5, 133.1, 25.0; IR (KBr) ν: 1773, 1732, 1645, 1434, 1372 cm-1;
HRMS (ESI): m/z calcd: 328.0564 [M+H]+; Found: 328.0559.
2d (eluted with a mixture of petroleum ether and ethyl acetate.
1
2k as a white solid (123 mg, 31%): mp 253-254 °C; H NMR (300
MHz, CDCl3, ppm): δ 4.59 (s, 6H), 2.27 (s, 3H); 13C NMR (100 MHz,
DMSO-d6, ppm): δ 162.1, 133.4, 78.0, 74.9, 28.0; IR (KBr) ν: 1783,
1732, 1638, 1380 cm-1; HRMS (APCI): m/z calcd: 400.0570 [M+H]+;
Found: 400.0567. Single crystal was obtained by slow diffusion of
isopropyl ether into a solution of 2k in DMF.
1
White solid, 78 mg, 34%): mp 298-299 °C; H NMR (400 MHz,
CDCl3, ppm): δ 3.89 (q, J = 7.2 Hz, 6H), 1.33 (t, J = 7.2 Hz, 9H); 13C
NMR (125 MHz, CDCl3, ppm): δ 162.5, 133.6, 34.4, 13.7; IR (KBr) ν:
1773, 1723, 1637, 1376 cm-1; HRMS (ESI): m/z calcd: 392.0859
[M+Na]+; Found: 392.0851.
Supporting Information
2e (eluted with a mixture of petroleum ether and ethyl acetate.
White solid, 202 mg, 37%): mp 288-289 °C; H NMR (400 MHz,
CDCl3, ppm): δ 4.67 (sep, J = 6.8 Hz, 3H), 1.54 (d, J = 6.8 Hz, 18H);
IR (KBr) ν: 1773, 1725, 1633, 1342 cm-1; HRMS (ESI): m/z calcd:
434.1328 [M+Na]+; Found: 434.1323.
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2019xxxxx.
1
Acknowledgement
2f (eluted with a mixture of petroleum ether and ethyl acetate.
White solid, 77 mg, 45%): mp 206-207 °C; H NMR (300 MHz,
We thank National Natural Science Foundation of China
(21772203, 21761132024, 21521002, 21871276), and Chinese
Academy of Sciences (QYZDJ-SSW-SLH023) for financial support.
Q.-Q.W. also thanks the Thousand Young Talents Program for
support. We thank Prof. Jieping Zhu from EPFL for helpful
discussion on the reaction mechanism.
1
CDCl3, ppm): δ 3.79 (t, J = 6.0 Hz, 6H), 1.82-1.70 (m, 6H), 0.97 (t, J
= 7.3 Hz, 9H); 13C NMR (75 MHz, CDCl3, ppm): δ 162.7, 133.5, 40.9,
21.6, 11.4; IR (KBr) ν: 1776, 1724, 1388, 1360 cm-1; HRMS (ESI):
m/z calcd: 434.1323 [M+Na]+; Found: 434.1321. Single crystal was
obtained by recrystallization from a hot solution of 2f in a mixture
of water and AcOH.
2g (eluted with a mixture of DCM and acetone. White solid, 81
mg, 63%): mp 250-251 °C; 1H NMR (400 MHz, CDCl3, ppm): δ 7.61
(s, 3H), 7.44-7.40 (m, 6H), 7.18 (t, J = 7.8 Hz, 3H), 4.90 (s, 6H); 13C
NMR (125 MHz, DMSO-d6, ppm): δ 163.2, 139.1, 133.4, 131.2,
131.0, 130.8, 127.3, 122.3, 41.5; IR (KBr) ν: 1776, 1731, 1637,
1571, 1473 cm-1; HRMS (APCI): m/z calcd: 789.8824 [M+H]+;
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Wang et al.
(The following will be filled in by the editorial staff)
Manuscript received: XXXX, 2019
Manuscript revised: XXXX, 2019
Manuscript accepted: XXXX, 2019
Accepted manuscript online: XXXX, 2019
Version of record online: XXXX, 2019
Chin. J. Chem. 2019, 37, XXX－XXX
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Entry for the Table of Contents
Page No.
Benzene Triimides (BTIs): Facile Synthesis and
Self-Assembly Study
A facile and efficient synthetic strategy for benzene triimides (BTIs) was developed, and the use of
BTIs as versatile building blocks for self-assembly was demonstrated.
De-Hui Tuo,+[a,b] Qing He,+[a] Qi-Qiang Wang,*[a,b]
Yu-Fei Ao,[a] and De-Xian Wang*[a,b]
a Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of
Molecular Recognition and Function, Institute of Chemistry, Chinese
Academy of Sciences, Beijing, 100190, China
E-mail: qiqiangw@iccas.ac.cn; dxwang@iccas.ac.cn
b University of Chinese Academy of Sciences, Beijing 100049, China
Chin. J. Chem. 2019, template
© 2018 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
This article is protected by copyright. All rights reserved.