Synthesis of perylene-bridged bis(dibenzo-24-crown-8) and its assembly behavior with a fullerene-based secondary dibenzylammonium salt

Article abstract of DOI:10.1007/s11426-010-4066-0

This paper reports the synthesis of a perylene-bridged bis(crown ether) through the condensation reaction between primary amine-armed dibenzo-24-crown-8 and 3,4,9,10-perylenetetracarboxylic dianhydride. Pseudorotaxane with a perylene moiety at the wheel and a fullerene unit in the middle of the axle was prepared, which was evidenced by ¹H NMR and fluorescence experiments. Subsequent investigations show that the formation and disassociation of the pseudorotaxane can be controlled by the alternating addition of KPF₆ and 18-crown-6, following the change of the florescence intensity of perylene.

Full text of DOI:10.1007/s11426-010-4066-0

SCIENCE CHINA
Chemistry
September 2010 Vol.53 No.9: 1982–1986
doi: 10.1007/s11426-010-4066-0
• ARTICLES •
Synthesis of perylene-bridged bis(dibenzo-24-crown-8) and its
assembly behavior with a fullerene-based secondary
dibenzylammonium salt
YAO HaiQing, ZHANG HengYi, HAN Min, DING ZhiJun, ZHANG ZhiJun & LIU Yu*
State Key Laboratory of Elemento-Organic Chemistry; Department of Chemistry, Nankai University, Tianjin 300071, China
Received April 29, 2010; accepted May 11, 2010
This paper reports the synthesis of a perylene-bridged bis(crown ether) through the condensation reaction between primary
amine-armed dibenzo-24-crown-8 and 3,4,9,10-perylenetetracarboxylic dianhydride. Pseudorotaxane with a perylene moiety at
the wheel and a fullerene unit in the middle of the axle was prepared, which was evidenced by 1H NMR and fluorescence ex-
periments. Subsequent investigations show that the formation and disassociation of the pseudorotaxane can be controlled by
the alternating addition of KPF6 and 18-crown-6, following the change of the florescence intensity of perylene.
crown ether, perylene, fullerene, pseudorotaxane
and optical properties owing to the ability of remarkable
1 Introduction
acceleration of photoinduced charge separation and decel-
eration of charge recombination in donor-fullerene systems
[10]. In order to construct fullerene-containing supramolecular
assemblies and advanced materials, fullerene has been in-
corporated into various systems such as porphyrins [11],
ferrocene [12], and hydroquinone [13]. The self-assembly
of fullerene-based molecules has aroused much interest in
the construction of more complex two- and three-dimen-
sional systems [14].
Dibenzo-24-crown-8 (DB24C8) can form 1:1 complexes
with the dialkylammonium cations. This unique binding
model has been utilized to construct various supramolecular
assemblies containing DB24C8 and dialkylammonium salts
[15]. Recently, we reported a reversible luminescent lantha-
nide switch based on this binding model [16] and a bistable
[3] rotaxane with intramolecular charge-transfer behavior
[17]. Herein, we synthesized a new perylene-bridged bis-
(DB24C8) host molecule (1), and constructed a pseudoro-
taxane system including 1 and a fullerene-based secondary
dibenzylammonium cation (2) (Figure 1). The reversible
fluorescence process of the pseudorotaxane can be modulated
Since 1950, perylene bisimide derivatives have found high
grade industrial applications [1] as pigments due to their
favorable combination of insolubility and migrational sta-
bility, light- and weather-fastness, thermal stability and
chemical inertness. Recently, perylene derivatives as n-type
semiconductors are also found to be promising compounds
for applications in optical [2] and electronic devices [3],
such as electrophotography [4], organic field effect transis-
tors [5], photovoltaic devices [6], and organic solar cells [7].
The intrinsic insolubility of perylene bisimides is the main
barrier for synthesis, purification and application. To pre-
pare soluble perylene bisimide dyes, Langhals [8] and Sey-
bold et al. [9] provided two successful strategies. The first
way is to introduce solubilizing substituents at the imide
nitrogen, and the other way is to introduce substituents at
the carbocyclic scaffold in the so-called bay-area.
Fullerene C60 possesses unique and attractive electronic
*Corresponding author (email: yuliu@nankai.edu.cn)
© Science China Press and Springer-Verlag Berlin Heidelberg 2010
chem.scichina.com
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YAO HaiQing, et al. Sci China Chem September (2010) Vol.53 No.9
1983
Figure 1 Structure of host 1 and guest 2.
by controlling the binding and release of the guest molecule 2.
3.83 (m, 8H), 3.92 (m, 8H), 4.18 (m, 8H), 6.88 (d, 1H), 6.88
(m, 4H), 7.33 (dd, 1H), 7.42 (d, 1H), m/z 657 [M+Na]+.
2 Experimental
N-(2-Aminoethyl)-6,7,9,10,12,13,20,21,23,24,26,27-dodecahy-
drodibenzo[b,n][1,4,7,10,13,16,19,22]octaoxacyclo-tetraco-
sine-2-carboxamide (5)
2.1 Materials and apparatus
Compound 4 was dissolved in 10 mL CHCl3, and the mix-
ture was stirred at room temperature. 4 mL of CF3COOH
was added dropwise. The stirring was continued overnight
and followed by evaporation of the solvent. The residue was
washed with hexane for three times. The crude product was
dissolved in CH3OH and the pH of the solution was ad-
justed to 8 by NaOH solution. The crude product was puri-
fied by silica-gel column chromatography using CHCl3/
CH3OH (5/1) (v/v) as the eluent to give product 5 (0.5 g,
3,4,9,10-Perylene dianhydride (Sigma-Aldrich company),
4-carboxylic-aciddibenzo-24-crown-8 (3) [18], compounds
6 [19], 7 [19] and the fullerene-based secondary diben-
zylammonium salt (2) [20] were prepared according to the
previously reported procedure. Chloroform and dichloro-
methane were redistilled and kept with 4 Å molecular sieve.
Acetonitrile is refluxed for 10 h in the presence of K2CO3
and KMNO4, stirred with a proper amount of P2O5 over-
night, and then distilled at 81–82 C. All the other chemi-
cals were commercially available.
1
90%); H NMR (400 MHz, CDCl3, 298 K)  2.95 (t, 2H),
1H NMR spectra were recorded on a Varian Mercury
VX400 spectrometer. Fluorescence spectra were measured
with JASCO FP-750 spectrometer. ESI-MS was performed
on Thermofinnigan LCQ Advantage LC-MS. MALDI-TOF
was performed on Bruker Autoflex III.
3.48 (t, 2H), 3.82 (m, 8H), 3.92 (m, 8H), 4.17 (m, 8H), 6.83
(d, 1H), 6.88 (m, 4H), 7.30 (dd, 1H), 7.41 (d, 1H), m/z 557
[M+Na]+.
Compound 1
Compounds 7 (300 mg, 0.3 mmol) and 5 (500 mg, 0.9 mmol)
were dissolved in 6 mL isopropanol, and then 0.1 mL
triethylamine was added. The mixture was refluxed under
N2 atmosphere for two days. The mixture was cooled to
room temperature and followed by evaporation of the sol-
vent. The crude product was purified by silica-gel column
chromatography using CHCl3/CH3OH (20/1) (v/v) as the
2.2 Synthesis of host 1
tert-Butyl 2-(6,7,9,10,12,13,20,21,23,24,26,27-dodecahydro-
dibenzo[b,n] [1,4,7,10,13,16,19,22] octaoxacyclotetracosine-
2-carboxamido)ethylcarbamate (4)
4-Carboxylic-aciddibenzo-24-crown-8 (3) (2.0 g, 4.1 mmol),
tert-butyl-2-aminoethyl carbamate (0.7 g, 4.6 mmol), N,N′-
dicyclohexylcarbodiimide (1.4 g, 6.8 mmol) and a little of
N,N-dimethylamino pyridine were dissolved in dry CHCl3
and the mixture was stirred in an ice bath for 12 h. The re-
action mixture was filtered. The filtrate was washed with
water twice, and dried over anhydrous sodium sulfate. Then
the solvent was removed at reduced pressure to give a white
residue. The residue was purified by silica-gel column
chromatography using CHCl3/CH3OH (20/1) (v/v) as the
1
eluent to give red powder 1 (300 mg, 50%); H NMR (400
MHz, CDCl3, 298 K)  1.28 (s, 36H), 3.67 (m, 12H), 3.72
(m, 12H), 3.82 (m, 12H), 4.02 (m, 12H), 4.28 (m, 4H), 6.78
(d, 8H) 6.85 (m, 8H), 7.18 (m, 4H), 7.25 (d, 8H), 7.50 (s,
4H), 7.99 (s, 4H) 13C NMR (400 MHz, CDCl3, 298 K) 
167.11, 164.16, 155.92, 152.89, 151.35, 148.85, 148.55,
147.34, 132.85, 127.17, 126.68, 122.09, 121.41, 120.90,
120.30, 119.62, 119.53, 119.39, 119.17, 114.01, 112.59,
71.35, 71.22, 71.16, 69.90, 69.68, 69.32, 69.23, 69.12, 34.38,
31.46. MS (MALDI-TOF) m/z: Anal. calcd C118H128O26N4:
[M+Na]+: 2040.8743, found [M+Na]+: 2040.8766.
1
eluent to give product 4 (1.4 g, 50%); H NMR (400 MHz,
CDCl3, 298 K)  1.42 (s, 9H), 3.40 (t, 2H), 3.52 (t, 2H),

1984
YAO HaiQing, et al. Sci China Chem September (2010) Vol.53 No.9
3.3 Fluorescence spectra of the interaction of 1 with 2
3 Results and discussion
Benefiting from the fascinating fluorescence property of
perylene, the host 1 displays satisfactory luminescent emis-
sion in a CHCl3:CH3CN = 2:1 (v/v) solution (Figure 4).
When excited at 510 nm, 1 showed two emission peaks at
620 nm (00) and a shoulder peak at 675 nm (01) [21].
When 22 equiv of the guest 2 was added to the solution, the
fluorescence emission at 620 nm of 1 was significantly
quenched to 75% of its original intensity. Instead of 2 with a
compound bearing the C60 moiety but without secondary
dibenzyl-ammonium unit, the luminescence of 1 slightly
decreased, which is attributed to the absorption of C60 ex-
isting at 450–750 nm. In addition, dibenzylammonium
hexafluorophosphate does not influence the luminescence of
1. These combined observations suggest that both the C60
unit and the dibenzylammonium cation are two prerequi-
sites to quench the fluorescence emission of 1. That indi-
cates the interaction of 1 with 2 leads to the formation of the
pseudorotaxane [1+2], so a PET process from perylene of 1
to the C60 moiety of 2 occurs due to the adjacence of C60
with perylene.
3.1 Synthesis
The synthetic pathway of 1 is shown in Figure 2. Compound
5 was obtained by DCC condensation of 4-carboxylic-
ciddibenzo-24-crown-8 (3) with tert-butyl-2-aminoethyl
carbamate, followed by CF3COOH reduction of the Boc-
protected group. 3,4,9,10-Perylene tetracarboxylic dianhy-
dride is insoluble in organic solvent. To improve its solubil-
ity, its bay-area was substituted by four chlorine atoms by
reacting with HSO3Cl, the propyl substituents were intro-
duced through reaction with propylamine. Compound 6 was
obtained by introducing four tert-butyl phenols at the bay-
area. Subsequent hydrolyzation of 6 with a base produced
compound 7. Finally, the target compound 1 was obtained
by the reaction of 5 with 7 in isopropanol using triethyl-
amine as the base. Owing to those soluble substitutions,
compound 1 possesses very good solubility in organic solvent.
3.2 1H NMR spectra of the complex of 1 with 2
To obtain in-depth mechanistic insight into the complexa-
tion between host 1 and guest 2, we performed H NMR
1
3.4 Reversible fluorescence switch
experiments. Figure 3 shows the signals of some pro-
tons moved apparently upon complexation. The Ha proton
in 2 shifted downfield from 3.90 to 4.62 ppm. This may be
attributed to the hydrogen bond interaction between Ha and
oxygen atoms of the crown ether. The resonances of the Hc
proton in 2 split into two equal parts. A half of them shifted
upfield, while the other remained unchanged. This means
that a half of 2 was located in the ring of the crown ether,
while the other did not bind with 1. In addition, the signals
of protons in crown ethers (3.4–4.5 ppm) and perylene (8.06
ppm) split apparently, indicating that the distance between
C60 and the perylene unit became close after complexation.
These spectral changes validate the formation of the pseu-
dorotaxane [1+2].
The binding behavior of 24C8 and the dialkylammonium
cation can be switched reversibly by various external stim-
uli, such as pH changes and competition binding. The asso-
ciation constants of DB24C8 with K+ and dialkylammonium
cations are 7.6 × 103 and 1.2 × 103 M1, respectively, while
that of 18-crown-6 (18C6) with K+ is 1.3 × 106 M1 [21].
From those data, we might deduce reasonably that the dial-
kylammonium cation in DB24C8 could be replaced by K+
upon the addition of KPF6 to the solution of the pseudoro-
taxane [1+2], and then the supramolecular assembly could
be reproduced upon the addition of 18-crown-6. To evi-
dence this assumption, we performed the fluorescent ex-
periments of the pseudorotaxane [1+2] in the absence and
Figure 2 Synthetic routes to host 1. (a) DCC, DMAP, BocNHCH2CH2NH2,CHCl3, 12 h, 50%. (b) TFA, 12 h, 90%. (c) (1) HSO3Cl, I2, 20 h, 40%, ; (2)
CH3CH2CH2NH2, H2O/CH3CH2CH2OH, 8 h, 99%. (3) ArOH, KCO3, NMP, 8 h, 90%. (d) KOH/H2O, CH3CHOHCH3, 12 h, 78%. (e) N(Et)3, CH3CHOHCH3,
2 d, 50%.

YAO HaiQing, et al. Sci China Chem September (2010) Vol.53 No.9
1985
emission was restored (91%). This observation suggests that
the dialkylammonium cation in DB24C8 was replaced by
K+ and the PET process from the perylene moiety to C60
was suppressed. To check the reversibility of this process,
18-crown-6 was added to the solution. The luminescence
quenching was reproduced again as a proof of regeneration
of the pseudorotaxane supramolecular assembly. The process
can be repeated several times. These experiments demon-
strate that the fluorescence of the pseudorotaxane [1+2] can
be switched in a reversible manner by external chemical
stimuli.
4 Conclusions
Figure 3 Partial 1H NMR spectra of (400 MHz, CD3CN/CDCl3 =1/2, 298
K, [1]0 = 3 mM) (a) 1, (b) 1 and 2.0 equiv of 2, and (c) 2 (Hcu: peak of the
uncomplex; Hcc: peak of the complex; *: peak of CDCl3).
In conclusion, a perylene-bridged bis(dibenzo-24-crown-8)
1 and a guest molecule 2 containing C60 unit have been
synthesized. The binding behavior and the photophysical
behavior of the resultant pseudorotaxane between 1 and 2
1
have been investigated through H NMR and fluorescence
spectra. The results obtained indicate that the fluorescence
of 1 was quenched significantly in the presence of 2, which
is attributed to a PET from perylene of 1 to the C60 moiety
of 2 in this pseudorotaxane system. The reversible fluores-
cence process can be modulated by controlling the binding
and release of the guest molecules by adding K+ or 18C6,
respectively. It is an effective strategy to control the fluo-
rescent behavior of perylene through external chemical
stimuli.
This work was supported by the National Basic Research Program of
China (973 Program) (2006CB932900) and the National Natural Science
Foundation of China (20932004 and 20772063).
Figure 4 The fluorescence spectra of compound 1 with increasing con-
centration of 2 (CHCl3:CH3CN = 2:1, 295 K); [1] =1×105 M and [2]=1×
105 to 2.2 × 104 M. ex = 510 nm.
1
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