Synthesis of novel supramolecular triads bearing a H-bonded perylene bisimide core

Article abstract of DOI:10.1016/j.tet.2012.07.015

Two novel hydrogen-bonded (H-bonded) triads consisting of triazine derivatives complexed with a perylene bisimide core were synthesized and characterized. NMR, UV/vis, and fluorescence spectra of these supramolecular triads confirmed the formation of stro

Full text of DOI:10.1016/j.tet.2012.07.015

Tetrahedron 68 (2012) 7926e7931
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Synthesis of novel supramolecular triads bearing a H-bonded perylene bisimide
core
*
Yesudoss Christu Rajan, Muthaiah Shellaiah, Ching-Ting Huang, Hsin-Chieh Lin, Hong-Cheu Lin
Department of Materials Science and Engineering, National Chiao Tung University, Hsinchu 30049, Taiwan, ROC
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 6 April 2012
Received in revised form 28 June 2012
Accepted 6 July 2012
Available online 16 July 2012
Two novel hydrogen-bonded (H-bonded) triads consisting of triazine derivatives complexed with
a perylene bisimide core were synthesized and characterized. NMR, UV/vis, and fluorescence spectra of
these supramolecular triads confirmed the formation of strong multiple H-bonding, which were also
proven to be nano-sized H-aggregates by X-ray diffraction (XRD) measurements.
Ó 2012 Elsevier Ltd. All rights reserved.
Keywords:
Hydrogen-bonded
Supramolecular triads
Perylene bisimide
Aryl amines
H-aggregates
1. Introduction
construction of three-dimensional supramolecular architectures in
both chemical and biological systems.8,9
During the past few decades, nanostructural aggregates of or-
ganic molecules have become significant topics due to their
promising applications in light-emitting diodes, photovoltaic cells,
sensors, lasers, field emitters, and field-effect transistors.1e4 Now-
adays intensive efforts to develop methods for producing organic
aggregation materials with low-dimensional structures, such as
nanowires, nanotubes, and nanorods, are of great importance in the
development of optoelectronic and nanoelectronic devices. These
novel aggregation structures and materials have been driven by
their unique electronic properties, as well as by the processing
advantages of organic materials relative to inorganic materials.
Supramolecular concept has attracted increasing attention in
macromolecular science, as one can design new supramolecular
architectures with interesting morphologies derived from non-
covalent interactions like hydrogen bonding, Van der Waals
2. Design and synthetic strategy
Supramolecular control over dye arrangement is important for
improving the performance of existing optoelectronic devices and
for creating new dye-based materials. Perylene bisimides (PBI)
have been widely applied as red dyes for industrial purposes owing
to their favorable chemical, light, and thermal stabilities.10e12 Self-
assembly, photophysical, and photochemical properties of perylene
bisimides forming complementary triple H-bonded interactions
were extensively studied.13,14
Recently, aggregates made from perylene bisimides (PBI) have
attracted increasing interests, since these dyes exhibit high quan-
tum yields, good photostability, and versatile building blocks for
functional supramolecular structures.15 Several reports revealed
that perylene bisimides formed H and J type aggregates with var-
ious triazine based donors.16e18 Nowadays, aryl amines have been
commonly used in optoelectronic materials because of their good
electron donating and transporting capabilities.19e23 To the best of
our knowledge, there are no reports on the studies of supramo-
lecular nano aggregations between perylene bisimides and aryl
amines. Herein, as shown in Fig. 1, we report for the first time, the
construction of nano-sized H-aggregates mediated by supramo-
lecular interactions of two novelly synthesized dodecyl trialkoxy
diaryl and triaryl amine triazine donors (compounds 12 and 16)
H-bonded with a perylene bisimide acceptor (PBI).
forces,
pep
stackings, and dipoleedipole interactions.5 Among
these interactions, hydrogen bonds with higher binding energies
were created as one of the most important forces to be used for the
design of various molecular aggregates.6,7 Since hydrogen bonding
is moderately strong, selective, more specific, and highly directional
in both solutions and surfaces, they are widely used in the
* Corresponding author. Tel.: þ886 3 5712121x55305; fax: þ886 3 5724727;
e-mail address: linhc@mail.nctu.edu.tw (H.-C. Lin).
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2012.07.015

Y.C. Rajan et al. / Tetrahedron 68 (2012) 7926e7931
7927
formation of hydrogen bonding between the donors (12 and 16)
and acceptor (PBI). These results indicated that the multiple
H-bonds were formed between the donors and central acceptor
(PBI).25
(a)
Fig. 1. Structures of 12, PBI, and 16.
PBI
60
5-Bromo-1,2,3-tris(dodecyloxy)benzene (4) (Scheme S1,
Supplementary data) and PBI were prepared according to the
literature.24,25 As shown in Scheme S2 (Supplementary data), ni-
tration of compound 5 with nitric acid and acetic acid gave com-
3172
12- PBI- 12
12
3320
40
pound 6.26 Demethylation of compound
6 using pyridine
hydrochloride at 200 ꢀC for 3 h afforded compound 7.27 Alkylation
of compound 7 gave compound 8,24 and reduction of compound 8
using PdeC and hydrazine hydrate led to the corresponding amine
(9).28 Synthesis of bis[1,2,3-tris(dodecyloxy)phenyl]amine (10)
was achieved by the application of BuchwaldeHartwig coupling
reaction,29 which involves the amination of compounds 4 and 9 in
the presence of Pd(OAc)2, P(t-Bu)3, and Cs2CO3. In order to
synthesize donor 12 (see Scheme 1), compound 10 was
treated with cyanuric chloride in the presence of DIPEA followed
by the nucleophilic substitution of chloride on the triazine
ring by n-butylamine.30 Compound 10 was coupled with
4-bromobenzonitrile and further refluxed with dicyandiamide
using 2-methoxyethanol as solvent to obtain donor 16.12
3434
20
0
3400
3200
3000
2800
2600
Wavenumber (cm-1)
80
60
40
20
0
(b)
PBI
3172
16- PBI- 16
Cl
(i) DIPEA, THF, 0oC, 2h
N
N
3328
10
12
Cl
N
Cl
(ii) BuNH2, NaHCO3,
Dioxane, 100oC, 24 h
11
16
CN
3405
CN
Pd(OAc) ,
2
P(t-Bu)3, Cs CO
2
3
C
C
H
O
O
N
OC
H
12 25
10
12 25
Toluene, 110oC, 72h
H
OC
H
H
12 25
12 25
Br
OC
H
12 25
OC
12 25
13
3400
3200
3000
2800
2600
14
Wavenumber (cm-1)
H
N
Fig. 2. FT-ATR-IR spectra of (a) compounds 12 and PBI, and complex 12ePBIe12 (2:1);
(b) compounds 16 and PBI, and complex 16ePBIe16 (2:1) in CH2Cl2 solutions.
NH
NH
KOH, 2-methoxy ethanol
130oC, 12 h
N
2
15
The formation of H-bonds in supramolecular complexes
12ePBIe12 and 16ePBIe16 and the interactions of PBI with 12 and
16 were also investigated by 1H NMR spectroscopic titrations in
CDCl3 (Fig. 3).32e35 The concentration of PBI was kept constant
(1ꢂ10ꢁ5 M) throughout the experiment and the changes in chem-
ical shifts were observed as a function of increasing concentrations
for compounds 12 and 16.12 As shown in Fig. 3, the peak at
16
Scheme 1. Synthesis of donors 12 and 16.
3. Results and discussion
d¼8.44 ppm was assigned to the NeH protons of acceptor PBI.
In order to verify the H-bonded interactions among moieties of
supramolecular complexes, FTIR experiments were proceeded. The
FT-ATR-IR spectra of compounds 12, 16, and PBI in CH2Cl2 (see
Fig. 2) showed the free NH stretching band at 3434, 3405, and
3172 cmꢁ1, respectively. The NH stretching bands of complexes
12ePBIe12 and 16ePBIe16 (2:1 stoichiometry) in CH2Cl2 were
observed at 3320 and 3328 cmꢁ1, respectively, which confirmed the
When acceptor PBI was complexed with various equivalents of
donor 12, the chemical shifts of the amidic proton in PBI changed
from 8.44 to 8.72e9.20 ppm (see Fig. 3a). The consecutive shifts to
lower magnetic fields were due to the decreased electron densities
of the protons involved in hydrogen bonding. Similarly, the
chemical shifts of NeH protons in PBI changed from 8.44 to
8.70e9.16 ppm as PBI was complexed with various equivalents of

7928
Y.C. Rajan et al. / Tetrahedron 68 (2012) 7926e7931
9.3
9.2
9.1
9.0
8.9
8.8
8.7
8.6
8.5
8.4
0
12-PBI-12
16-PBI-16
5
10
15
20
25
Concentration (mM)
Fig. 4. 1H NMR shifts of NeH protons in PBI for supramolecular triads formed by 12
and 16, where the concentration of PBI was fixed at 10 mM.
(a)
0
2.0
1.5
2.4 equi. (12)
1.0
0.5
0.0
Fig. 3. 1H NMR spectra of PBI (10 mM) titrated with compounds (a) 12 and (b) 16
(0e25 mM) in CDCl3 at room temperature.
16 (see Fig. 3b). During these titrations, some up-field shifts in
triazine NH protons of 12 and 16 were found, but the triazine NH
protons were not distinguishable because of the overcrowding in
their alkyl chain regions.36
350
400
450
500
550
600
650
700
The downfield shifts of the amidic protons in PBI were due to
the formation of supramolecular triads 12ePBIe12 and
16ePBIe16, which were characteristics of the multiple H-bonded
complexes.1 As shown in Fig. 4, the analysis of the amidic protons in
acceptor PBI as a function of increasing concentrations for com-
pounds 12 and 16 supported the supramolecular (1:2) binding
model for the H-bonded complexes.
Wavelength (nm)
(b)
0
2.0
1.5
1.0
0.5
0.0
Figs. 5 and 6 show the UV/vis and PL spectra of H-bonded
complexes 12ePBIe12 and 16ePBIe16. Upon the aliquot addition
of donor 12 to PBI, a hypsochromic shift with absorption from
562 nm to 557 nm and emission from 591 nm to 586 nm were
observed. Similarly, accompanied by blue shift H-bonded complex
16ePBIe16 showed significant decreases of absorbtion from
562 nm to 556 nm and emission from 591 nm to 585 nm. The long
alkoxy chains substituted at the donor moiety played a vital role in
decreasing the absorption and emission of both complexes
12ePBIe12 and 16ePBIe16. The titration analysis of both supra-
molecular triads (12ePBIe12 and 16ePBIe16) showed the for-
mation of 2:1 H-bonded triads. Results of UV/vis and PL titrations
also revealed that both H-bonded triads 12ePBIe12 and
16ePBIe16 further stacked into H-aggregates.31 H-aggregates
exhibited broad absorption bands, which were blue shifted with
respect to the donor absorption.15 The fluorescence of H-aggregates
was weak or lacking due to the fact that the optically accessible
exciton states were in the upper region of the exciton band and
2.4 equiv. (16)
350
400
450
500
550
600
650
700
Wavelength (nm)
Fig. 5. UV/vis titration spectra of complexes (a) 12ePBIe12 and (b) 16ePBIe16. The
concentration of PBI in methyl cyclohexane was kept constant at 1ꢂ10ꢁ5 mol/L upon
the addition of 12 and 16 with different concentrations (0e2.4 equiv, with an equal
span of 0.2 equiv).

Y.C. Rajan et al. / Tetrahedron 68 (2012) 7926e7931
7929
0.2
(a)
0.3
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
1000
500
(a)
2.4 equiv. (12)
0.4
0.5
0.6
0.7
0.8
0
0.9
0.0
0.5
1.0
1.5
2.0
2.5
3.0
[12] / Equiv.
0.2
0
550
(b)
600
650
700
0.3
0.4
0.5
0.6
0.7
0.8
Wavelength (nm)
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
1000
500
(b)
2.4 equiv. (16)
0
0.9
0.0
0.5
1.0
1.5
2.0
2.5
3.0
[16] / Equiv.
Fig. 7. Job’s plots for determining the stoichiometry of (a) 12ePBIe12 and (b)
16ePBIe16 based on normalized absorbance intensity at 562 nm as a function of
equivalents.
0
550
600
650
700
16ePBIe16 are also given in Table 1. The average particle sizes of H-
bonded complexes 12ePBIe12 and 16ePBIe16 are ca. 9.5 A. Based
ꢀ
Wavelength (nm)
on the aggregation size (w1 nm) of 12ePBIe12 or 16ePBIe16
Fig. 6. PL titration spectra of complexes (a) 12ePBIe12 and (b) 16ePBIe16. The
concentration of PBI in methyl cyclohexane was kept constant at 1ꢂ10ꢁ5 mol/L upon
the addition of 12 and 16 at different concentrations (0e2.4 equiv, with an equal span
of 0.2 equiv). Excitation wavelength¼591 nm.
ꢀ
acquired by XRD data along with the rough layer thickness of 3.5 A
in a planar perylene structure,39 we can estimate that the number
of ca. three-layer molecules were packed in the aggregates of
12ePBIe12 or 16ePBIe16 due to the strong
a planar structure in PBI.
pep stacking of
their population was quickly transferred to low-lying exciton states,
possessing no transition dipole to the ground state.37 As shown in
Fig. 7a and b, equivalent values of 2.07 and 1.99 were obtained by
two plots of normalized absorbance intensities at 562 nm as
a function of equivalents for compounds 12 and 16, respectively,
indicating a 1:2 (PBIe12/16) stoichiometric complex formation.
The binding constants were calculated from standard deviation and
linear fit of Fig. S1.
4. Conclusion
In conclusion, novel H-bonded supramolecular triads of dodecyl
trialkoxy diaryl and triaryl amine triazine derivatives with perylene
bisimides were successfully synthesized and characterized. NMR,
IR, UV/vis, and PL spectra confirmed the existence of strong mul-
tiple H-bonded interactions between the donors (12 and 16) and
acceptor (PBI). Interestingly, X-ray diffraction measurements
proved the formation of nano-sized particles by H-aggregates in
both H-bonded triads 12ePBIe12 and 16ePBIe16, which could be
of importance for future applications. Well-defined nano-sized H-
aggregates might be valuable for the development of novel func-
tional materials utilized in nano-technological devices.
Fig. 8 shows the X-ray diffraction (XRD) patterns for compounds
12, 16, and PBI, along with H-bonded triads 12ePBIe12 and
16ePBIe16, on glass substrate at room temperature. The donors
(12 and 16) and acceptor (PBI) possessed strong Bragg’s diffraction
but after the complexation of aryl amines 12 and 16 with PBI, de-
crease in XRD intensities was observed with broad peaks. The XRD
peaks are 11.6ꢀ, 20.4ꢀ for 12ePBIe12 and 13.0ꢀ, 23.1ꢀ for
16ePBIe16. The calculated values of lattice spacings for H-bonded
complexes are illustrated in Table 1. The particle size of complexes
12ePBIe12 and 16ePBIe16 were calculated using Scherrer for-
5. Experimental section
5.1. General information
mula.36,38 Particle size (D)¼(0.9
l)/(b cos q), where l, b, and q rep-
ꢀ
resent the X-ray wavelength (1.5406 A), full width at half maximum
(FWHM) of diffraction peaks, and Bragg diffraction angle at room
temperature, respectively. The FWHM values of 12ePBIe12 and
All anhydrous reactions were carried out avoiding moisture by
standard procedures under nitrogen atmosphere. The solvents
were dried by distillation over appropriate drying agents. Reactions

7930
Y.C. Rajan et al. / Tetrahedron 68 (2012) 7926e7931
16, and PBI were dissolved in methyl cyclohexane at a concentra-
PBI
(a)
tion of 1ꢂ10ꢁ5 mol/L.
5.2. Bis(3,4,5,-tridodecylphenyl)amine (10)
16
In dry and degassed toluene (30 mL), Pd(OAc)2 (130 mg,
0.6 mmol) and P(t-Bu)3 (2.4 mL, 1.2 mmol, 10% in hexane) were
introduced. After 15 min stirring, compound 4 (5.2 g, 7.4 mmol),
compound 9 (4 g, 6 mmol), and Cs2CO3 (5.6 g, 12.5 mmol) were
added. The solution was refluxed for 4 days, cooled to room tem-
perature, and diluted with CH2Cl2 (100 mL). Crude mixture was
filtered through Celite, evaporated to dryness, and purified on silica
gel column (25% CH2Cl2/hexanes) to obtain 10 (4.7 g, 60%) as light
12
yellow solids. Mp 47e50 ꢀC; 1H NMR (300 MHz, CDCl3)
d 0.87 (t,
18H, J¼6.6 Hz, Me), 1.27 (br, 96H, CH2) 1.40e1.47 (m, 12H, CH2),
5
10
15
20
θ (degree)
25
30
1.69e1.82 (m, 12H, CH2), 3.87e3.91 (m, 12H, CH2), 5.39 (s, 1H, NH),
2
6.25 (s, 4H, ArH); 13C NMR (75 MHz, CDCl3)
132.67, 139.30, 153.64.
d 69.03, 73.56, 97.23,
16-PBI-16
12-PBI-12
30
(b)
5.3. N2,N4-Dibutyl-N6,N6-bis(3,4,5-tris(dodecyloxy)phenyl)-
1,3,5-triazine-2,4,6-triamine (12)
N,N-Diisopropylethylamine (DIPEA) of 0.32 mL (1.87 mmol) was
added to a solution of 0.3 g (1.17 mmol) 2,4,6-trichloro-1,3,5-
triazine 11 in anhydrous tetrahydrofuran (THF) (30 mL). The re-
action mixture was cooled to 0 ꢀC, and a solution of 10 (1.5 g,
1.17 mmol) in THF (20 mL) was added dropwise over 1 h at this
temperature. After completion of the addition, the reaction mixture
was warmed to room temperature, and stirred for an additional
12 h until the starting material disappeared. The resulting white
precipitate was filtered off and the filtrate was evaporated under
reduced pressure. The obtained crude compound (1.5 g, 90%) was
dissolved in dioxane (60 mL) mixed with n-butylamine (0.5 mL,
5 mmol) and NaHCO3 (0.5 g, 6 mmol), and then the solution was
refluxed for 12 h. The reaction mixture was poured into 200 mL of
water and extracted three times with CH2Cl2. The combined or-
ganic extract was washed with water, brine, dried over anhydrous
MgSO4, and evaporated to dryness and purified on silica gel column
(20%EtOAc/hexanes) to afford 12 (1.4 g, 85%) as a low melting solid.
5
10
15
20
(degree)
θ
25
2
Fig. 8. XRD patterns of (a) compounds 12, 16, and PBI, (b) complexes 12ePBIe12 and
16ePBIe16, on glass substrates at room temperature.
Table 1
FMHM values, lattice d-spacings, and particle sizes of H-bonded complexes
12ePBIe12 and 16ePBI-16
1H NMR (300 MHz, CDCl3)
d
0.87 (t, 24H, J¼7.5 Hz, Me), 1.26 (br,
H-bonded complex
12ePBIe12
16ePBIe16
96H, CH2) 1.41 (br, 16H, CH2), 1.69e1.81 (m, 12H, CH2), 3.17 (br, 4H,
NHCH2), 3.82e3.95 (m, 12H, OMe), 4.80 (br, 2H, NH), 6.44 (s, 4H,
q1
q2
q1
q2
2
q
(ꢀ)
FWHM (ꢀ)
11.6
8.1
7.6
20.4
9.1
4.4
13.0
7.2
6.8
23.1
10.3
3.9
ArH); 13C NMR (75 MHz, CDCl3):
d 14.10, 20.02, 22.68, 26.16, 29.36,
31.92, 40.35, 69.03, 73.38, 106.81, 135.79, 139.40, 152.60, 166.24, and
179.61. HRMS-ESI: (Mþ) found 1496.3556. C95H174N6O6 requires
1496.3573. Anal. found: C, 75.12; H, 11.74; N, 5.59. C95H174N6O6
requires : C; 76.25; H, 11.72; N, 5.72.
ꢀ
d-spacing (A)
ꢀ
Particle size (A)
9.9
8.9
11.1
7.9
were monitored by TLC inspection on silica gel plates. Column
chromatography was generally performed on silica gel. 1H and 13C
NMR were recorded on a 300 MHz spectrometer. The chemical
5.4. 4-(Bis(3,4,5-tris(dodecyloxy)phenyl)amino)benzonitrile
(14)
shifts (
in hertz and relative to TMS (
denote single, double, ternary, quadruple, multiple, and broad, re-
spectively) and chloroform-d ( 7.26) and ( 77.0) were used as
d
) are reported in parts per million and coupling constants (J)
In dry and degassed toluene (20 mL), Pd(OAc)2 (34 mg,
0.156 mmol) and P(t-Bu)3 (0.6 mL, 0.3 mmol, 10% in hexane) were
introduced. After 15 min stirring, 4-bromobenzonitrile 13 (0.28 g,
7.0 mmol), compound 10 (2 g, 1.56 mmol), and Cs2CO3 (2.2 g,
6 mmol) were added. The solution was refluxed for 3 days, cooled
to room temperature, and diluted with CH2Cl2 (100 mL). The crude
mixture was filtered through Celite, evaporated to dryness, and
purified on silica gel column (20%CH2Cl2/hexanes) to afford light
yellow solid 14 (1.6 g, 72%). Mp 56e59 ꢀC; 1H NMR (300 MHz,
d
0.00) for 1H NMR (s, d, t, q, m, and br
d
d
reference for 1H and 13C NMR, respectively. Mass spectra were
obtained on HR-ESI and FAB mass spectrometer. Elemental analysis
was carried out by Elemental Vario EL. FT-ATR spectra were mea-
sured by using Perkin Elmer spectrum 100 series spectrometer.
Spectra were collected at a resolution of 4 cmꢁ1 using a deuterated
triglycine sulfate detector by averaging four scans. Absorption and
fluorescence spectra were measured on V-670 spectrophotometer
and F-4500 fluorescence spectrophotometer, respectively. X-ray
diffraction (XRD) studies of compounds on glass substrates were
CDCl3)
d
0.87 (t, 18H, J¼6.9 Hz, Me), 1.25 (br, 96H, CH2) 1.38e1.48
(m, 12H, CH2), 1.69e1.77 (m, 12H, CH2), 3.77e3.96 (m, 12H, OMe),
6.29 (s, 4H, ArH), 6.97 (d, 2H, J¼9 Hz, ArH), 7.62 (d, 2H, J¼9 Hz, ArH).
13C NMR (75 MHz, CDCl3)
d 69.55, 73.89, 101.88, 105.46, 119.26,
performed using monochromatic CuK
a
1 radiation. Compounds 12,
120.28, 133.39, 136.38, 141.25, 152.03, 154.14.

Y.C. Rajan et al. / Tetrahedron 68 (2012) 7926e7931
7931
7. Archer, E. A.; Gong, H.; Krische, M. J. Tetrahedron 2001, 57, 1139e1159.
5.5. 6-(4-(Bis(3,4,5-tris(dodecyloxy)phenyl)amino)phenyl)-
1,3,5-triazine-2,4-diamine (16)
8. Sanchez, L.; Martin, N.; Guldi, D. M. Angew. Chem., Int. Ed. 2005, 44, 5374e5382.
9. Zhang, J.; Hoeben, F. J. M.; Pouderoijen, M. J.; Schenning, A. P. H.; Meijer, E. W.;
De Schryver, F. C.; De Feyter, S. Chem.dEur. J. 2006, 12, 9046e9055.
€
€
10. Schmidt-Mende, L.; Fechtenkotter, A.; Mullen, K.; Moons, E.; Friend, R. H.;
In a round-bottom flask, compound 14 (1.5 g, 1 mmol) and
dicyandiamide 15 (0.1 g, 1.3 mmol) were dissolved in 2-
methoxyethanol (30 mL). After adding KOH (0.34 g, 6 mmol), the
solution was stirred at 100 ꢀC for 24 h. After cooling the reaction
mixture to room temperature, 100 mL of brine was added and the
aqueous phase was extracted three times with dichloromethane
(100 mL). The organic fractions were collected and dried over
MgSO4. After evaporation of the solvent, the product was purified
with silica gel column chromatography (30% EtOAc/hexanes) to
afford 16 (0.6 g, 38%) light yellow powders. 1H NMR (300 MHz,
MacKenzie, J. D. Science 2001, 293, 1119e1122.
€
11. Wurthner, F.; Thalacker, C.; Sautter, A. Adv. Mater. 1999, 11, 754e758.
12. Schenning, A. P. H. J.; Jonkheijm, P.; Peeters, E.; Meijer, E. W. J. Am. Chem. Soc.
2001, 123, 409e416.
€
13. Wurthner, F.; Thalacker, C.; Diele, S.; Tschierske, C. Chem.dEur. J. 2001, 7,
2245e2253.
€
14. Yagai, S.; Seki, T.; Karatsu, T.; Kitamura, A.; Wurthner, F. Angew. Chem., Int. Ed.
2008, 47, 3367e3371.
15. Ambrosek, D.; Marciniak, H.; Lochbrunner, S.; Tatchen, J.; Li, X.-Q.; Wurthner, F.;
Kuhn, O. Phys. Chem. Chem. Phys. 2011, 13, 17649e17657.
16. Neuteboom, E. E.; Beckers, E. H. A.; Meskers, S. C. J.; Meijer, E. W.; Janssen, R. A.
J. Org. Biomol. Chem. 2003, 1, 198e203.
€
17. Wurthner, F.; Sautter, A. Org. Biomol. Chem. 2003, 1, 240e243.
CDCl3)
d
0.87 (t, 18H, J¼7.5 Hz, Me), 1.25 (br, 96H, CH2) 1.37e1.48
18. Boom, T. V. D.; Hayes, R. T.; Zhao, Y.; Bushard, P. J.; Weiss, E. A.; Wasielewski, M.
R. J. Am. Chem. Soc. 2002, 124, 9582e9590.
19. Thelakkat, M. Macromol. Mater. Eng. 2002, 287, 442e461; (b) Ito, A.; Sakamaki,
D.; Ichikawa, Y.; Tanaka, K. Chem. Mater. 2011, 23, 841e850.
(m, 12H, CH2), 1.69e1.77 (m, 12H, CH2), 3.76e3.97 (m, 12H), 5.19 (s,
4H, NH2). 6.03 (s, 4H, ArH), 7.03 (d, 2H, J¼8.7 Hz, ArH), 8.12 (d, 2H,
J¼8.7 Hz, ArH). 13C NMR (75 MHz, CDCl3)
d 69.28, 73.70, 104.70,
20. Shirota, Y. J. Mater. Chem. 2000, 10, 1e25.
124.59,128.30,129.51,135.20,142.38,141.40,153.71,169.63,172.15.
HRMS-FAB: (Mþ), found 1459.2565. C93H162N6O6 requires 1459.26.
Anal. found: C, 76.12; H, 11.16; N, 5.82. C93H162N6O6 requires: C;
76.49; H, 11.18; N, 5.75.
21. Shirota, Y.; Kageyama, H. Chem. Rev. 2007, 107, 953e1010.
22. Fan, L.; Xu, Y.; Tian, H. Tetrahedron Lett. 2005, 46, 4443e4447.
23. Zhao, Y.; Wasielewski, M. R. Tetrahedron Lett. 1999, 40, 7047e7050.
24. (a) Li, W. S.; Yamamoto, Y.; Fukushima, T.; Saeki, A.; Seki, S.; Tagawa, S.; Masu-
naga, H.; Sasaki, S.; Takata, M.; Aida, T. J. Am. Chem. Soc. 2008, 130, 8886e8887.
25. (a) Liu, Y.; Xiao, S.; Li, H.; Li, Y.; Liu, H.; Lu, F.; Zhuang, J.; Zhu, D. J. Phys. Chem. B
2004, 108, 6256e6260.
Acknowledgements
26. Gong, J.; Huang, K.; Wang, F.; Yang, L.; Feng, Y.; Li, H.; Li, X.; Zeng, S.; Wu, X.;
€
Stockigt, J.; Zhao, Y.; Qu, J. Bioorg. Med. Chem. 2009, 17, 3414e3425.
The authors thank the National Science Council of Taiwan (ROC)
through NSC99-2113-M-009-006-MY2 for the financial support.
They are grateful to Mr. R. Thangavel and Mr. R. Saminathan for
their valuable technical assistance.
27. Percec, V.; Bura, T. K.; Lodde, M.; Fu, Q.; Venkatachalapathy, S.; Balagurusamy,
K.; Heine, P. A. Chem.dEur. J. 2003, 9, 921e935.
28. Lincker, F.; Bourgun, P.; Masson, P.; Didier, P.; Guidoni, L.; Bigot, J. Y.; Nicoud, J.
F.; Donnio, B.; Guillon, D. Org. Lett. 2005, 7, 1505e1508.
29. Bordeau, G.; Lartia, R.; Metge, G.; Debuisschert, C. F.; Charra, F.; Fichou, M. P. T. J.
Am. Chem. Soc. 2008, 130, 16836e16837.
30. Lu, Z.; Gamez, P.; Mutikainen, I.; Turpeinen, U.; Reedijk, J. Cryst. Growth Des.
Supplementary data
2007, 7, 1669e1671.
€
31. Schenning, A. P. H. J.; Herrikhuyzen, J. V.; Jonkheijm, P.; Chen, Z.; Wurthner, F.;
Supplementary data associated with this article can be found in
the online version, at http://dx.doi.org/10.1016/j.tet.2012.07.015.
Meijer, E. W. J. Am. Chem. Soc. 2002, 124, 10252e10253.
32. Liu, Y.; Li, Y.; Jiang, L.; Gan, H.; Liu, H.; Li, Y.; Zhuang, J.; Lu, F.; Zhu, D. J. Org.
Chem. 2004, 69, 9049e9054.
33. Liu, Y.; Zhuang, J.; Liu, H.; Li, Y.; Lu, F.; Gan, H.; Jiu, T.; Wang, N.; He, X.; Zhu, D.
ChemPhysChem 2004, 5, 1210e1215.
References and notes
34. Miura, A.; De Feyter, S.; De Schryver, F. C.; Wurthner, F. Org. Biomol. Chem. 2005,
3, 414e422.
35. Wurthner, F.; Thalacker, C.; Sautter, A.; Schartl, W.; Ibach, W.; Hollricher, O.
1. Liu, H.; Xu, J.; Li, Y.; Li, Y. Acc. Chem. Res. 2010, 43, 1496e1508.
2. Liu, H.; Li, Y.; Xiao, S.; Gan, H.; Jiu, T.; Li, H.; Jiang, L.; Zhu, D.; Yu, D.; Xiang, B.;
Chen, Y. J. Am. Chem. Soc. 2003, 125, 10794e10795.
€
€
Chem.dEur. J. 2000, 6, 3871e3886.
36. Muthaiah, S.; Rajan, Y. C.; Lin, H. C. J. Mater. Chem. 2012, 22, 8976e8987.
37. Fink, R. F.; Pfister, J.; Zhao, H. M.; Engels, B. Chem. Phys. 2008, 346, 275e285.
38. Yagai, S.; Iwashima, T.; Kishikawa, K.; Nakahara, S.; Karatsu, T.; Kitamura, A.
Chem.dEur. J. 2006, 12, 3984e3994.
39. Tang, M. L.; Oh, J. H.; Reichardt, A. D.; Bao, Z. J. Am. Chem. Soc. 2009, 131,
3733e3740.
3. Coropceanu, V.; Cornil, J.; da Silva Filho, D. A.; Olivier, Y.; Silbey, R.; Bredas, J. L.
Chem. Rev. 2007, 107, 926e952.
4. Zang, L.; Che, Y.; Moore, J. F. Acc. Chem. Res. 2008, 41, 1596e1608.
5. Brunsveld, L.; Folmer, B. J. B.; Meijer, E. W.; Sijbesma, R. P. Chem. Rev. 2001, 101,
4071e4098.
6. Sijbesma, R. P.; Meijer, E. W. Chem. Commun. 2003, 5e16.