Synthesis and supramolecular self-assembly of coil-rod-coil molecules: The relationship between self-assembled nanostructures and molecular structures

Article abstract of DOI:10.1002/asia.201000567

Herein, the relationship between the supramolecularly self-assembled nanostructures and the chemical structures of coil-rod-coil molecules is discussed. A series of nonamphiphilic coil-rod-coil molecules with different alkyl chains, central mesogenic grou

Full text of DOI:10.1002/asia.201000567

FULL PAPERS
DOI: 10.1002/asia.201000567
Synthesis and Supramolecular Self-Assembly of Coil-Rod-Coil Molecules:
The Relationship between Self-Assembled Nanostructures and Molecular
Structures
Yulan Chen, Fan Zhang, Bo Zhu, Yang Han, and Zhishan Bo*[a]
Abstract: Herein, the relationship be-
tween the supramolecularly self-assem-
bled nanostructures and the chemical
structures of coil-rod-coil molecules is
discussed. A series of nonamphiphilic
coil-rod-coil molecules with different
alkyl chains, central mesogenic groups,
and chemical linkers were designed
and synthesized. The solvent-mediated
micron sized belts, needle-like micro-
crystals, and amorphous structures. The
self-assembling behaviors of these coil-
rod-coil molecules have been systemat-
ically investigated to reveal the rela-
tionship between the supramolecularly
self-assembled nanostructures and their
chemical structures. With respect to the
formation of rolled-up nanotubes by
self-assembly of coil-rod-coil molecules,
we have systematically investigated the
following three influencing structural
factors: 1) the alkyl chain length; 2) the
central mesogenic group; (3) the linker
type. These studies disclosed the key
structural features of coil-rod-coil mol-
ecules for the formation of rolled-up
nanotubes.
Keywords: coil-rod-coil
·
nano-
supramolecular
self-assembling
of
tubes · self-assembly · superstruc-
tures · supramolecular chemistry
these coil-rod-coil molecules resulted
in rolled-up nanotubes, nanofibers, sub-
Introduction
low-dimensional nanostructures, especially tubular struc-
tures, from both the academic and technologic stand-
points,[1,2,14–20] these initial results inspired us to further ex-
plore what is the rational molecular design for the supra-
molecular self-assembly of low-dimensional nanostructures,
especially tubular structures. The nonamphiphilic coil-rod-
coil molecule TB is constituted of three parts: 1) a central
rigid terphenylene segment; 2) two secondary amido func-
tional groups; 3) two flexible alkyl chains. The central ter-
phenylene segment has a strong tendency to aggregate
through p–p overlapping; the two secondary amido groups
can form the intermolecular translation-related hydrogen
bonding. The synergistic effects of these two kinds of inter-
actions make TB self-assemble to form one-layer supra-
molecular nanosheets. The one-layer nanosheets have a
strong tendency to either stack to form lamellar sheets or to
form rolled-up-type nanotubes.
To understand which parts play a key role in formation of
rolled-up nanotubes by self-assembly of coil-rod-coil mole-
cules, herein we report the design, synthesis, and self-assem-
bly of three types of nonamphiphilic coil-rod-coil molecules.
We have systematically investigated the following three in-
fluencing structural factors:[21–25] 1) the alkyl chain length;
2) the central mesogenic group; 3) the linker type. These
studies disclosed the key structural features of coil-rod-coil
molecules for the formation of rolled-up nanotubes.
The self-assembly of well-defined nanoscale architectures,
especially tubular structures, by small organic molecules is
of great current interest and a challenging topic in the areas
of chemistry and material sciences.[1–6] In comparison with
other nanostructures, such as ribbons and fibrils, the self-as-
sembly of high-aspect nanotubes is considered most chal-
lenging as strict conditions are required and only a few ex-
amples have been reported.[7–12] In previous work, we have
reported the hierarchically supramolecular self-assembly of
a small organic nonamphiphilic coil-rod-coil molecule p-ter-
phenylen-1,4’’-ylenebis(dodecanamide) (TB) to form a new
kind of rolled-up organic nanotube from its nanosheets pre-
cursor.[13] The nanotubes are micrometers in length and
have diameters in the range of 90 to 120 nm, with approxi-
mately 20-nm-thick walls and an aspect ratio up to 300 with
a novel scrolling pattern. Considering the importance of
[a] Y. Chen, F. Zhang, B. Zhu, Y. Han, Prof. Dr. Z. Bo
College of Chemistry
Beijing Normal University
Beijing 100875 (P.R. China)
Fax : (+86)10-8261-8587
E-mail: zsbo@iccas.ac.cn
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201000567.
226
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Chem. Asian J. 2011, 6, 226 – 233

Results and Discussion
lene core, two undecane chains at two ends, and different
linkers. The syntheses of Type-1 molecules (TB-1, TB-7, TB-
8, TB-9, TB-11, and TB-16) are shown in Scheme 2. Starting
Molecular Design and Synthesis
As shown in Scheme 1, the coil-rod-coil molecules used for
supramolecular self-assembly can be categorized into three
types according to their structural features. The first type
(Type 1) includes molecules containing the central p-terphe-
nylene core, two secondary amido functional groups, and
alkyl chains with different lengths at two ends; the second
one (Type 2) includes molecules containing two secondary
amido functional groups, different central mesogenic groups,
and two undecane chains at the two ends; the third one
(Type 3) includes molecules containing a central p-terpheny-
Scheme 2. The synthetic routes for Type-1 molecules. Reaction condi-
tions: a) EDC·HCl, HOBt, Et3N, CHCl2, RT, 24h; b) Pd
NaHCO3, THF, H2O, N2, reflux, 24h. THF=tetrahydrofuran.
ACHTUNGTRENNUNG(PPh3)4,
from commercially available alkyl carboxylic acid and 4-bro-
moaniline, their coupling reaction was carried out by using
1-ethyl-3-(3-dimethylamino)propylcarbodiimide hydrochlo-
ride (EDC·HCl) and 1-hydroxybenzotriazole (HOBt) as
mild coupling reagents to afford amides 1a–g in yields of
35–97%. Suzuki–Miyaura cross-coupling of 1a–g and ben-
zene-1,4-diboronic acid 1,3-propanediol ester with PdACHTUNGTRENNUNG(PPh3)4
as the catalyst precursor afforded the desired molecules TB-
1, TB-7, TB-8, TB-9, TB-11, and TB-16, respectively, in
yields of 66–81%. The syntheses of Type-2 molecules (AB-
1, AB-2, DB, TTB, and Hex-TB) are shown in Scheme 3.
Miyaura cross-coupling of 1e and bis(pinacolato)diboron
with PdACHTNURGTNE(UNG dppf)2Cl2 as the catalyst precursor afforded N-(4-pi-
nacolatoboronphenyl)dodecan amide (2) in a yield of 98%.
The Suzuki–Miyaura cross-coupling of 2 and 1e furnished p-
diphenylen-1,4’’-ylenebis(dodecanamide) (DB) in a yield of
83%. The synthesis of acetylene-containing compound AB-
1 started from amide 1e, its reaction with trimethylsilyl acet-
ylene under Sonogashira coupling conditions afforded TMS-
protected acetylene, and followed by deprotection of the
TMS group with tetrabutylammonium fluoride (TBAF), fur-
nished the acetylene-terminated compound 4 in an overall
yield of 83%. Sonogashira cross-coupling of 1e and 4 af-
forded the acetylene-containing compound AB-1 in a yield
of 31%. The diacetylene-containing compound AB-2 was
synthesized in a yield of 63% by Glaser coupling of acety-
lene-terminated amide 4. The p-tetraphenylen-1,4”-ylene-
bis(dodecanamide) (TTB) was synthesized in a yield of
79% by a Suzuki–Miyaura coupling of 1e and 4,4’-biphenyl-
diboronic acid. Compound Hex-TB bearing two hexyl
chains at the central benzene ring was obtained in 83%
yield by Suzuki–Miyaura cross-coupling of 1e and 2,5-dihex-
ylbenzene-1,4-diboronic acid. The syntheses of Type-3 mole-
cules are shown in Scheme 4. The coupling of dodecylamine
and 4-bromobenzoic acid by using EDC·HCl and HOBt as
mild coupling reagents afforded 4-bromo-N-dodecylbenza-
mide (5) in a yield of 98%. Suzuki–Miyaura cross-coupling
Scheme 1. Carton model of a coil-rod-coil molecule and the chemical
structures of Type-1, Type-2, and Type-3 molecules.
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FULL PAPERS
of 5 and benzene-1,4-diboronic acid 1,3-propanediol ester
afforded the desired coil-rod-coil molecule TB-r-10 in a
yield of 92%. Ester-linked molecule TB-10-E was acquired
by a Suzuki–Miyaura coupling of benzene-1,4-diboronic acid
1,3-propanediol ester and 4-bromophenyl dodecanoate (6),
which was prepared by coupling 4-bromophenol and dodec-
anoic acid with 4-(dimethylamino)pyridinium 4-toluenesul-
fonate (DPTS) and DCC as mild coupling agents. All inter-
mediates were unambiguously characterized by 1H and
13C NMR spectroscopy and elemental analysis. With the ex-
ception of Hex-TB and TB-10-E, all the coil-rod-coil mole-
cules are almost insoluble in any organic solvent at room
temperature, thus making routine NMR spectroscopic char-
acterization impossible. These coil-rod-coil molecules pre-
cipitated from the solvent mixture during the reaction. The
precipitates were thoroughly washed with THF and water to
remove the soluble impurities and inorganic salts, the resi-
due was dissolved in hot THF and filtrated, and the resulting
precipitate from the hot THF filtrates were collected by fil-
tration to afford the desired products as a colorless solid.
The high purity of the products was confirmed by combus-
tion analysis. Compound TB-10 was selected for solid-state
13C NMR characterization (Figure S1 in the Supporting In-
formation), and the result confirmed the expected structure.
The introduction of two hexyl chains on the central benzene
ring significantly improved the solubility of Hex-TB in
1
common organic solvents. H and 13C NMR spectra of Hex-
TB and TB-10-E also confirmed the expected structures.
Scheme 3. The synthetic routes for type-2 molecules. Reaction condi-
Self-Assembly of Coil-Rod-Coil Molecules
tions: a) Pd
NaHCO3, THF, H2O, N2, reflux, 24h; c) trimethysilylacetylene, Pd-
(PPh3)2Cl2, CuI, NH(iPr)2, THF, N2, 808C, 24h; d) TBAF, CH2Cl2; e) 1e,
Pd(PPh3)2Cl2, CuI, NH(iPr)2, THF, N2, 808C, 24h; f) Pd(PPh3)2Cl2, CuI,
NH(iPr)2, THF, O2, RT, 24h; g) 1,4-biphenyldiboronic acid, Pd(PPh3)4,
NaHCO3, THF, H2O, N2, reflux, 24h; h) 2,5-dihexylphenyldiboronic acid
ester, Pd(PPh3)4, NaHCO3, THF, H2O, N2, reflux, 24h.
ACHTUNGTRENNUNG(dppf)Cl2, KOAc, DME, N2, 808C, 24h; b) 1e, PdCAHTUNGTREN(NGUN PPh3)4,
The solvent-mediated supramolecular self-assembly experi-
ments were performed by following the previously reported
procedures.[13] Typically, a suspension of coil-rod-coil mole-
cules in THF (0.1 mgmLÀ1) was heated to reflux until all
solids were completely dissolved to form a clear solution.
The solution was allowed to cool gradually to room temper-
ature, and it turned cloudy after about 1 hour. A drop of the
suspension was deposited onto the silicon substrate and
copper-grid coated with carbon film for SEM and TEM in-
vestigations, respectively. Owing to the extremely poor solu-
bility of compounds TTB and TB-r-10 in THF, only about
0.02 mgmLÀ1 was used to ensure that these two compounds
could be completely dissolved in refluxing THF. However,
owing to the good solubility of DB and TB-10-E in THF, a
higher concentration (1.0 mgmLÀ1) was used for the self-as-
sembly study. Hex-TB exhibited very good solubility in THF
at room temperature; its self-assembling experiment was
therefore carried out with xylene as the solvent.
A
ACHTUNGTRENNUNG
A
R
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
Influence of the Alkyl Chain Length on the Self-Assembly
Behavior
Scheme 4. The synthetic routes for Type-3 molecules. Reaction condi-
tions: a) EDC·HCl, HOBt, Et3N, CHCl2, RT, 24h; b) 1,4-phenyldiboronic
To investigate the influence of the coil part on the self-as-
sembly behavior, type-1 series molecules (TB-1, TB-7, TB-8,
TB-9, TB-11, and TB-16) with alkyl chain length from C2 to
C17 were synthesized and used for supramolecular self-as-
acid ester, PdACHTUNGTRENNUNG(PPh3)4, NaHCO3, THF, H2O, N2, reflux, 24h; c) DCC,
DMAP, TsSO3H·H2O, CH2Cl2, RT, 24h; d) 1,4-phenyldiboronic acid
ester, PdACHTUNGTRENNUNG(PPh3)4, NaHCO3, THF, H2O, N2, reflux, 24h.
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Self-assembly of coil-rod-coil molecules
sembling. There was a common feature for type-1 series
molecules, they all exhibited a concentration-dependent
self-assembling behavior as reported in our previous
paper,[13] namely, the self-assembly of the type-1 series mole-
cules at low concentration afforded exclusively rolled-up
nanotubes, at high concentration afforded thick layered
sheets, and in between afforded a mixture of nanotubes and
layered sheets. We have investigated the self-assembly of
rolled-up nanotubes by type-1 series molecules in details.
Following standard procedures, the supramolecular self-as-
sembly of type-1 series molecules in THF at a concentration
of 0.1 mgmLÀ1 furnished exclusively rolled-up nano-
tubes.[13,26–28] SEM images of nanotubes formed by solvent-
mediated supramolecular assembly of type-1 series mole-
cules (TB-1, TB-7, TB-8, TB-9, TB-11, and TB-16) are
shown in Figure 1. Even TB-1, which has a very short coil
Figure 2. TEM images of a) TB-1; b) TB-7; c) TB-8; d) TB-9; e) TB-11;
f) TB-16 nanotubes.
tion of the length of the flexible alkyl chains can cause the
change of the diameter and length of the self-assembled
nanotubes. These results indicated that the flexible alkyl
chain part did not play a key role in the hierarchical supra-
molecular assembly of nanotubes.
Influence of the Central Mesogenic Group on the Self-
Assembling Behavior
To investigate the influence of the central mesogenic group
on the self-assembly behavior, Type-2 series molecules (DB,
AB-1, AB-2, TTB, and Hex-TB) were synthesized and used
for supramolecular self-assembling. In contrast with Type-1
series molecules, Type-2 series molecules showed quite dif-
ferent self-assembling behaviors from one another. An air-
dried suspension of DB displayed ill-defined aggregates,
with only the quasi-1D assemblies (Figure 3a). Owing to the
weaker p–p attractive forces between the biphenyl units, the
supramolecular assembly of DB only afforded less-ordered
nanostructures. For TTB, the tetraphenylene scaffold has an
extremely strong tendency to aggregate through p–p over-
lap. As shown in Figure 3b, the self-assembly of TTB in
THF afforded 2D crystals. It is worth noting that a recent
paper has already reported a helical structure formed by
supramolecular assembly of phenylen-1,4-ylenebis (dodeca-
namide).[29] The supramolecular self-assembly of coil-rod-
Figure 1. SEM images of a) TB-1; b) TB-7; c) TB-8; d) TB-9; e) TB-11;
f) TB-16 nanotubes on silicon substrates.
part (C2), can self-assemble to form nanotubes. As observed
by SEM and TEM (Figure 2), the nanotubes formed by the
self-assembly of TB-1 are several hundreds of nanometers
long and about 60 nanometers in diameter. The TEM image
revealed that TB-1 nanotubes have a very small inner
hollow space and a thick tube wall. The self-assembled
nanotubes with TB-7, TB-8, TB-9, and TB-11 have a large
diameter distribution ranging from about 100 to 200 nm and
a large length distribution ranging from about one to tens of
micrometers. As observed by SEM and TEM, the self-as-
sembly of coil-rod-coil molecules (TB-16) carrying long flex-
ible alkyl chains afforded high aspect ratio nanotubes. From
the above-mentioned results, we could find that the varia-
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FULL PAPERS
Figure 4. SEM images of a) irregular needle-like microcrystals from the
self-assembly of TB-r-10 at low concentration; b) high aspect ratio micro-
fibrils from the self-assembly of TB-r-10 at a higher concentration.
self-assembly of Type-1 molecules, the self-assembly of TB-
r-10 in THF with a concentration of 0.02 mgmLÀ1 only af-
forded irregular needle-like microcrystals[25] (Figure 4a);
whereas the supramolecular self-assembly of TB-r-10 at a
higher concentration afforded high aspect ratio microfibrils
(Figure 4b). These experiments revealed that the linker be-
tween the central terphenylene unit and the two flexible
alkyl chains is also very crucial for the formation of rolled-
up nanotubes.
Through the above investigations, we could find that the
rolled-up nanotubes are closely related to 2D sheets. Coil-
rod-coil molecules that can self-assemble to form 2D sheets
at a high concentration always form rolled-up nanotubes at
a low concentration. If the self-assembly of coil-rod-coil
molecules forms nanobelts or nanofibrils, no rolled-up nano-
tubes can be formed. The rolled-up nanotubes always coex-
ist with 2D sheets, but never with nanofibrils or nanobelts.
Figure 3. SEM images of self-assembled nanostructures of a) DB;
b) TTB; c) AB-1; d) AB-2.
coil molecules AB-1 and AB-2 in THF only afforded irregu-
lar nanobelts as shown in Figure 3c and 3d.
We also studied the steric effect on the supramolecular as-
sembly behavior. Compound Hex-TB carrying two lateral
hexyl chains at the center phenyl group was also synthesized
and used for supramolecular self-assembly. The two bulky
lateral hexyl chains can prevent the central terphenylene
unit from close packing. As expected, Hex-TB is soluble in
THF and formed organogel in xylene. SEM and AFM
images of Hex-TB gel displayed a network structure com-
posed of nanoscale fibrous aggregates with a high aspect
ratio. These fibers are several micrometers long and with di-
ameters in the range of 50 to 300 nm, thereby reflecting the
hierarchical self-organization (Figure S2 in the Supporting
Information).
Conclusions
These experimental results revealed that the central ter-
phenylene segment of coil-rod-coil molecules played a very
crucial role for the formation of rolled-up nanotubes.
Herein, we have described the design and synthesis of a
series of non-amphiphilic coil-rod-coil molecules. We have
systematically investigated the influence of the following
three factors (the length of alkyl chains at two ends, the
type of central mesogenic group, and the linker between the
central mesogenic group and the alkyl chains) on the self-as-
sembling behaviors. We have found that the central meso-
genic group and the linkers play a key role in the self-assem-
bly of rolled-up nanotubes. Only coil-rod-coil molecules
with a p-terphenylene mesogenic group and two amide link-
ers with nitrogen atoms at the central p-terphenylene unit
can form rolled-up nanotubes through supramolecular self-
assembling. Variation of the length of alkyl chains at the
two ends (from C2 to C17) can modulate the diameter and
the length of the self-assembled nanotubes. The self-assem-
bly of other types of coil-rod-coil molecular structures can
only afford nanofibrils or nanobelts, but not rolled-up nano-
tubes. These studies disclosed the key structural features of
coil-rod-coil molecules for the formation of rolled-up nano-
tubes.
Influence of the Linker Type on the Self-Assembling
Behavior
To investigate the influence of the linker on the self-assem-
bly behavior, Type-3 series molecules (TB-10-E and TB-r-
10) were synthesized and used for supramolecular self-as-
sembly. Coil-rod-coil molecule (TB-10-E) with ester linkers
between the central p-terphenylene unit and the two flexible
alkyl chains was also designed and synthesized. In compari-
son with Type-1 and Type-2 series molecules with amide
linkers, TB-10-E shows much better solubility in common
organic solvents such as THF, chloroform, and methylene
chloride. As observed by SEM, the self-assembly of TB-10-
E in THF only afforded an amorphous film on silicon sub-
strate (Figure S3 in the Supporting Information). Coil-rod-
coil molecule TB-r-10, which has a central p-terphenylene
unit, two flexible alkyl chains, and two amide linkers with a
nitrogen atom on the alkyl chain, was also used for supra-
molecular self-assembly. By using similar conditions for the
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Self-assembly of coil-rod-coil molecules
a white solid (1.5 g, 79%). 1H NMR (CDCl3, 400 MHz): d=7.42 (s, 4H,
ArH), 7.15 (s, 1H, NH), 2.34 (t, 2H, CH2), 1.71 (m, 2H, CH2), 1.33–1.26
(m, 12H, CH2), 0.88 ppm (t, 3H, CH3); 13C NMR (CDCl3, 100 MHz): d=
171.60, 136.95, 131.89, 121.34, 116.72, 37.73, 31.82, 29.40, 29.34, 29.23,
25.54, 22.63, 14.08 ppm. Anal calcd for C16H24NBrO: C, 58.90; H, 7.41; N,
4.29; found: C 59.02, H 7.47, N 4.34.
Experimental Section
General Methods: The catalyst precursor, PdACHTNURTGNE(UNG PPh3)4, was prepared ac-
cording to the literature[30] and stored in a Schlenk tube under nitrogen.
Benzene-1,4-diboronic acid 1,3-propanediol ester[31] and 2,5-dihexylben-
zene-1,4-diboronic acid[32] were prepared according to literature proce-
dures. 1,4-Biphenyldiboronic acid was purchased from Lancaster Synthe-
sis. 1-Hydroxybenzotrizole (HOBt), 1-ethyl-3-(3-(dimethylamino) propyl)
carbodiimide hydrochloride (EDC·HCl) and dicyclohexylcarbodiimide
(DCC) were purchased from Shanghai Medpep. Other chemicals were
purchased from Aldrich or Acros and used without further purification.
Solvents were dried according to standard procedures. All reactions were
performed under an atmosphere of nitrogen and monitored by TLC with
silica gel 60 F254 (Merck, 0.2 mm). Column chromatography was carried
out on silica gel (200–300 mesh).
N-(4-bromophenyl)undecanamide (1d): The general procedure for amide
synthesis was followed. 4-Bromoaniline (1.38 g, 8.0 mmol), undecanoic
acid (1.0 g, 5.4 mmol), HOBt (0.87 g, 6.4 mmol), EDC·HCl (1.85 g,
9.7 mmol), dry CH2Cl2 (50.0 mL), and triethylamine (2.0 mL) were used.
Chromatography on silica gel eluting with CH2Cl2/n-hexane (3:1) afford-
1
ed 1d as a white solid (1.2 g, 66%). H NMR (CDCl3, 400 MHz): d=7.41
(s, 4H, ArH), 7.22 (s, 1H, NH), 2.34 (t, 2H, CH2), 1.71 (m, 2H, CH2),
1.31–1.25 (m, 14H, CH2), 0.88 ppm (t, 3H, CH3); 13C NMR (CDCl3,
100 MHz): d=172.07, 137.13, 132.05, 121.68, 116.98, 37.84, 32.04, 29.72,
29.64, 29.53, 29.46, 25.78, 22.83, 14.27 ppm. Anal calcd for C17H26NBrO:
C 60.00, H 7.70, N 4.12; found: C 60.01, H 7.70, N, 4.35.
Characterization: 1H and 13C NMR spectra were recorded on an AV400
spectrometer in CDCl3. Elemental analyses were performed on a Flash
EA 1112 analyzer. Scanning electron microscopy (SEM) was performed
on a JEOL model JSM-6700F FE-SEM and a Hitachi S-4800 FE-SEM
operating at 5 kV. Samples for SEM measurement were prepared by
dropping a THF suspension onto a silicon substrate followed by air
drying and coating with platinum. Transmission electron microscopy
(TEM) was performed on a Hitachi H-800 electron microscope operating
at 100 kV and a JEOL model JEM-2011 electron microscope operating
at 200 kV. Samples for TEM measurement were prepared by dropping
the THF suspension (0.1 mgmLÀ1) onto 200-mesh copper grids followed
by air drying. AFM images were recorded under ambient conditions by
using a Digital Instrument Multimode Nanoscope IIIA operating in the
tapping mode. Samples for AFM measurement were prepared by dipping
a silicon wafer into the gel phase for 15 min.
N-(4-bromophenyl)dodecanamide (1e): The general procedure for amide
synthesis was followed. 4-Bromoaniline (1.93 g, 11.2 mmol), lauric acid
(1.5 g, 7.5 mmol), HOBt (1.22 g, 9.0 mmol), EDC·HCl (2.58 g,
13.4 mmol), dry CH2Cl2 (60.0 mL), and triethylamine (2.0 mL) were used.
The crude product was precipitated in n-hexane and then filtrated. Flash
chromatography on silica gel eluting with CH2Cl2 afforded 1e as a white
solid (1.9 g, 72%). 1H NMR (CDCl3, 400 MHz): d=7 .42 (s, 4H, ArH),
7.18 (s, 1H, NH), 2.34 (t, 2H, CH2), 1.71 (m, 2H, CH2), 1.32–1.25 (m,
16H, CH2), 0.88 ppm (t, 3H, CH3); 13C NMR (CDCl3, 100 MHz): d=
171.87, 137.20, 132.06, 121.58, 116.89, 37.91, 32.07, 29.78, 29.65, 29.54,
29.50, 29.43, 25.75, 22.85, 14.29 ppm. Anal calcd for C18H28NBrO: C
61.34, H 7.99, N 4.21; found: C 61.02, H 7.97, N, 4.52.
N-(4-bromophenyl)tridecanamide (1 f): The general procedure for amide
synthesis was followed. 4-Bromoaniline (1.2 g, 7.0 mmol), tridecanoic
acid (1.0 g, 4.6 mmol), HOBt (0.76 g, 5.6 mmol), EDC·HCl (1.61 g,
8.4 mmol), dry CH2Cl2 (50.0 mL), and triethylamine (2.0 mL) were used.
Chromatography on silica gel eluting with CH2Cl2/n-hexane (3:1) afford-
ed 1 f as a white solid (0.9 g, 52%). 1H NMR (CDCl3, 400 MHz): d=7
.42(s, 4H, ArH), 7.09 (s, 1H, NH), 2.34(t, 2H, CH2), 1.71 (m, 2H, CH2),
1.33–1.25 (m, 18H, CH2), 0.88 ppm (t, 3H, CH3); 13C NMR (CDCl3,
100 MHz): d=171.81, 137.12, 132.05, 121.54, 116.89, 37.88, 32.05, 29.76,
29.61, 29.48, 29.40, 25.71, 22.82, 14.26 ppm. Anal calcd for C19H30NBrO:
C 61.95, H 8.21, N 3.80; found: C 61.92, H 8.29, N 3.58.
General Procedure for Amide Synthesis: A mixture of amine, acid,
HOBt, EDC·HCl, dry CH2Cl2, and triethylamine was stirred at room
temperature for 24 h. Water was added; the organic layer was separated,
washed successively with aqueous HCl (5m) solution and water, dried
over anhydrous Na2SO4, and evaporated to dryness. The crude product
was purified by silica gel chromatography.
General Procedure for Suzuki Cross-Coupling: A mixture of aryl bro-
mide, diboronic acid or diboronic acid ester, PdACTHNUGTRNEUNG(PPh3)4, NaHCO3, H2O,
and THF were charged sequentially in a Schlenk flask under a nitrogen
atmosphere and heated to reflux for 24 h. The precipitated white solid
was filtered, and washed with water and THF. The crude product was
then dissolved in refluxing THF, and followed by hot filtration.
N-(4-bromophenyl)stearicamide (1g): The general procedure for amide
synthesis was followed. 4-Bromoaniline (1.36 g, 7.9 mmol), stearic acid
(1.5 g, 5.3 mmol), HOBt (0.86 g, 6.4 mmol), EDC·HCl (1.8 g, 9.4 mmol),
dry CH2Cl2 (50.0 mL), and triethylamine (2.0 mL) were used. The crude
product was recrystallized with CH2Cl2 to afford a white solid (0.8 g,
35%). 1H NMR (CDCl3, 400 MHz): d=7.42(s, 4H, ArH), 7.14(s, 1H,
NH), 2.34(t, 2H, CH2), 1.71(m, 2H, CH2), 1.43–1.25 (m, 28H, CH2),
0.88 ppm (t, 3H, CH3); 13C NMR (CDCl3, 100 MHz): d=171.53, 137.02,
131.97, 121.34, 116.74, 37.84, 33.68, 31.95, 29.72, 29.49, 29.38, 29.28, 29.10,
25.56, 24.77, 22.72, 14.14 ppm. Anal calcd for C24H40BrNO: C 65.74, H
9.19, N 3.19; found: C 65.81, H 9.35, N 3.48.
N-(4-bromophenyl)propanamide (1a): The general procedure for amide
synthesis was followed. 4-Bromoaniline (2.0 g, 11.6 mmol), propanoic
acid (0.57 g, 7.7 mmol), HOBt (1.26 g, 9.3 mmol), EDC·HCl (2.67 g,
13.9 mmol), dry CH2Cl2 (50.0 mL), and triethylamine (2.0 mL) were used.
Chromatography on silica gel eluting with CH2Cl2/n-hexane (4:1) afford-
1
ed 1a as a white solid (1.7 g, 97%). H NMR (CDCl3, 400 MHz): d=7.41
(s, 4H, ArH), 7.30 (s, 1H, NH), 2.38 (m, 2H, CH2), 1.23 ppm (t, 3H,
CH3); 13C NMR (CDCl3, 100 MHz): d=172.51, 137.17, 132.06, 121.64,
116.92, 30.80, 9.77 ppm. Anal calcd for C9H10NBrO: C 47.39, H 4.42, N
6.14; found: C 47.49, H 4.43, N 5.94.
N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)dodecanamide
(2): A Schlenk tube was charged with 1e (0.45 g, 1.27 mmol), KOAc
(0.75 g, 7.6 mmol), bis(pinacolato)diboron (0.645 g, 2.54 mmol), Pd-
N-(4-bromophenyl)nonanamide (1b): The general procedure for amide
synthesis was followed. 4-Bromoaniline (2.0 g, 11.6 mmol), nonanoic acid
(1.23 g, 7.8 mmol), HOBt (1.26 g, 9.3 mmol), EDC·HCl (2.67 g,
13.9 mmol), dry CH2Cl2 (50.0 mL), and triethylamine (2.0 mL) were used.
Chromatography on silica gel eluting with CH2Cl2/n-hexane (4:1) afford-
AHCTUNGTREG(NNNU dppf)Cl2 (0.03 g, 0.038 mmol) and DMF (30 mL) and flushed with nitro-
gen. The mixture was stirred at 808C for 24 h under nitrogen. Ethyl ace-
tate (80 mL) was added and the mixture was washed with water (3ꢁ
50 mL) to remove DMF from the organic layer. The organic layer was
separated, dried over anhydrous Na2SO4, and evaporated to dryness. The
crude product was purified by flash silica gel chromatography eluting
with CH2Cl2 to afford 2 as a white solid (0.50 g, 98%). 1H NMR (CDCl3,
400 MHz): d=7.76 (d, 2H, ArH), 7.52 (d, 2H, ArH), 7.17 (s, 1H, NH),
2.35 (t, 2H, CH2), 1.71 (m, 2H, CH2), 1.33 (s, 12H, CH3), 1.29–1.25 (m,
16H, CH2), 0.88 ppm (t, 3H, CH3); 13C NMR (CDCl3, 100 MHz): d=
171.59, 140.68, 135.79, 118.56, 83.72, 37.90, 31.90, 29.60, 29.47, 29.38,
29.32, 29.27, 25.56, 25.16, 24.84, 22.68, 14.11 ppm. Anal calcd for
C24H40NBO3: C 71.81, H 10.04, N 3.49; found: C 71.27, H 10.06, N, 3.59.
1
ed 1b as a white solid (2.0 g, 82%). H NMR (CDCl3, 400 MHz): d=7.41
(s, 4H, ArH), 7.31 (s, 1H, NH), 2.34 (t, 2H, CH2), 1.69 (m, 2H, CH2),
1.28–1.26 (m, 10H, CH2), 0.87 ppm (t, 3H, CH3); 13C NMR (CDCl3,
100 MHz): d=171.80, 137.16, 132.07, 121.55, 116.89, 37.91, 31.96, 29.48,
29.42, 29.29, 25.73, 22.79, 14.25 ppm. Anal calcd for C15H22NBrO: C
57.70, H 7.10, N 4.49; found: C 57.84, H 7.23, N 4.58.
N-(4-bromophenyl)decanamide (1c): The general procedure for amide
synthesis was followed. 4-Bromoaniline (1.5 g, 8.7 mmol), decanoic acid
(1.0 g, 5.8 mmol), HOBt (0.94 g, 7.0 mmol), EDC·HCl (2.0 g, 10.4 mmol),
dry CH2Cl2 (50.0 mL), and triethylamine (2.0 mL) were used. Chroma-
tography on silica gel eluting with CH2Cl2/n-hexane (3:1) afforded 1c as
Chem. Asian J. 2011, 6, 226 – 233
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
231

Z. Bo et al.
FULL PAPERS
N-(4-ethylene
phenyl)dodecanamide
(4):
Pd
(PPh3)2Cl2
(36 mg,
diboronic acid ester (0.06 g, 0.244 mmol), PdACTHUGNTERN(NUG PPh3)4 (11 mg,
0.050 mmol) and CuI (19.3 mg, 0.01 mmol) were added to a dry Schlenk
flask, which was degassed and purged with nitrogen, 1e (1.8 g,
5.08 mmol), THF (12 mL) and HNACTHNUTRGNE(UGN iPr)2 (8 mL), and trimethysilylacety-
0.0095 mmol), NaHCO3 (0.82 g, 9.8 mmol), H2O (5 mL), and THF
(10 mL) were used to afford TB-9 as a white solid (0.11 g, 76%). Anal
Calcd for C40H56N2O2: C 80.49, H 9.46, N 4.69; found: C 79.99, H 9.38, N
4.69.
lene (0.87 mL, 6.09 mmol) were added by using a syringe. The mixture
was heated to 808C and stirred for 24 h. The solvent was removed under
vacuum, the residue was dissolved in CH2Cl2 and purified by flash silica
gel chromatography eluting with CH2Cl2 to give 3 as a white solid.
1H NMR (CDCl3, 400 MHz): d=7.47 (d, 2H, ArH), 7.41 (d, 2H, ArH),
7.13 (s, 1H, NH), 2.34 (t, 2H, CH2), 1.71 (m, 2H, CH2), 1.33–1.25 (m,
16H, CH2), 0.88 (t, 3H, CH3), 0.24 ppm (s, 9H, CH3). Tetrabutylammoni-
um fluoride (1.69 g, 6.46 mmol) was added dropwise to a solution of com-
pound 3 in 25 mL of CH2Cl2 at 08C. The mixture was stirred for 10 min
and purified by flash silica gel chromatography eluting with CH2Cl2 to
afford 4 as a white solid (1.26 g, 83%). 1H NMR (CDCl3, 400 MHz): d=
7.49 (d, 2H, ArH), 7.43 (d, 2H, ArH), 7.31 (s, 1H, NH), 3.03 (s, 1H,
CH), 2.34 (t, 2H, CH2), 1.71 (m, 2H, CH2), 1.33–1.25 (m, 16H, CH2),
0.88 ppm (t, 3H, CH3); 13C NMR (CDCl3, 100 MHz): d=171.45, 138.39,
132.89, 119.23, 117.49, 83.34, 37.83, 31.86, 29.56, 29.43, 29.32, 29.28, 29.22,
25.50, 22.64, 14.07 ppm. Anal calcd for C20H29NO: C 80.22, H 9.76, N,
4.68; found: C 80.04, H 9.68, N 4.66.
Terphenylene-bisdodecanamide (TB-10): The general procedure for
Suzuki cross-coupling was followed. 1e (0.200 g, 0.56 mmol), 1,4-phenyl-
diboronic acid ester (0.058 g, 0.23 mmol), PdACHTNUTRGNE(UNG PPh3)4 (11 mg,
0.0095 mmol), NaHCO3 (0.79 g, 9.4 mmol), H2O (5 mL), and THF
(10 mL) were used to afford TB-10 as a white solid (0.115 g, 78%). Anal
calcd for C42H60N2O2: C 80.72, H 9.68, N 4.48; found: C 80.43, H 9.59, N
4.41.
Terphenylene-bistridecanamide (TB-11): The general procedure for
Suzuki cross-coupling was followed. 1 f (0.200 g, 0.54 mmol), 1,4-phenyl-
diboronic acid ester (0.056 g, 0.23 mmol), PdACHTNUTRGNE(UNG PPh3)4 (10 mg,
0.0086 mmol), NaHCO3 (0.76 g, 9.0 mmol), H2O (5 mL), and THF
(10 mL) were used to afford TB-11 as a white solid (0.12 g, 81%). Anal
calcd for C44H64N2O2: C 80.93, H 9.88, N 4.29; found: C 80.24, H 9.75, N
4.16.
Terphenylene-bisstearicamide (TB-16): The general procedure for Suzuki
cross-coupling was followed. 1g (0.15 g, 0.34 mmol), 1,4-phenyldiboronic
4-Bromo-N-dodecylbenzamide (5): The general procedure for amide syn-
thesis was followed. 4-Bromobenzoic acid (2.0 g, 9.95 mmol), dodecana-
mine (2.2 g, 11.9 mmol), HOBt (1.6 g, 11.8 mmol), EDC·HCl (3.4 g,
17.7 mmol), dry CH2Cl2 (60.0 mL), and triethylamine (2.0 mL) were used.
Chromatography on silica gel eluting with CH2Cl2/n-hexane (3:1) afford-
ed 5 as a white solid (3.6 g, 98%). 1H NMR (CDCl3, 400 MHz): d=7.62
(d, 2H, ArH), 7.55 (d, 2H, ArH), 6.13 (s, 1H, NH), 3.43 (m, 2H, CH2),
1.60 (m, 2H, CH2), 1.33–1.25 (m, 18H, CH2), 0.88 ppm (t, 3H, CH3).
13C NMR (CDCl3, 100 MHz): d=166.60, 133.66, 131.71, 128.53, 125.93,
40.26, 31.91, 29.64, 29.63, 29.59, 29.55, 29.34, 27.01, 22.68, 14.11 ppm;
Anal calcd for C19H30NBrO: C 61.95, H 8.21, N, 3.80; found: C 62.02, H
8.19, N, 3.98.
acid ester (0.035 g, 0.14 mmol), PdACHTUNTRGNEUNG(PPh3)4 (6.6 mg, 0.0057 mmol),
NaHCO3 (0.48 g, 5.7 mmol), H2O (5 mL), and THF (10 mL) were used to
afford TB-16 as a white solid (0.076 g, 67%). Anal calcd for C54H84N2O2:
C 81.76, H 10.67, N 3.53 ; found: C 81.06, H 10.50, N 3.54.
DB: The general procedure for Suzuki cross-coupling was followed. 1e
(0.094 g, 0.265 mmol),
2
(0.1 g, 0.249 mmol), PdACHTNGUTERNNU(G PPh3)4 (5.4 mg,
0.0047 mmol), NaHCO3 (0.4 g, 4.7 mmol), H2O (5 mL), and THF
(10 mL) were used to afford DB as a white solid (0.113 g, 83%). Anal
calcd for C36H56N2O2: C 78.78, H 10.28, N 5.10; found: C 78.63, H 10.38,
N 5.09.
TTB: The general procedure for Suzuki cross-coupling was followed. 1e
(0.200 g, 0.56 mmol), 1,4-biphenyldiboronic acid (0.056 g, 0.23 mmol), Pd-
4-Bromophenyl dodecanoate (6):
A mixture of lauric acid (1.0 g,
AHCTNUGERT(GNNNU PPh3)4 (10 mg, 0.0086 mmol), NaHCO3 (0.79 g, 9.4 mmol), H2O (5 mL),
and THF (15 mL) were used to afford TTB as a white solid (0.131 g,
79%).
5.0 mmol), 4-bromophenol (1.3 g, 7.5 mmol), 4-(dimethylamino)pyridini-
um 4-toluenesulfonate (DPTS)[33] (1.76 g, 6 mmol), and CH2Cl2 (30 mL)
was stirred at room temperature for 1 h. A solution of DCC (1.8 g,
9.0 mmol) in CH2Cl2 (20 mL) was slowly added to this mixture. After the
addition was complete, the mixture was stirred at room temperature for
24 h. The urea precipitate was filtered off and the obtained solution was
evaporated to dryness. The residue was purified by chromatography on
silica gel eluting with CH2Cl2/n-hexane (1:2) to afford 6 as a white solid
(1.6 g, 90%). 1H NMR (CDCl3, 400 MHz): d=7.48 (d, 2H, ArH), 6.97
(d, 2H, ArH), 2.54 (t, 2H, CH2), 1.74(m, 2H, CH2), 1.41–1.19 (m, 16H,
CH2), 0.89 ppm (t, 3H, CH3); 13C NMR (CDCl3, 100 MHz): d=171.92,
149.82, 132.41, 123.39, 118.74, 34.94, 34.34, 31.91, 29.60, 29.45, 29.33,
29.24, 29.09, 24.88, 22.68, 14.10 ppm. Anal calcd for C18H27BrO2: C 60.85,
H 7.66, found: C 61.21, H 7.65.
Hex-TB: The general procedure for Suzuki cross-coupling was followed.
1e (0.42 g, 1.18 mmol), 2,5-dihexylphenyldiboronic acid ester (0.2 g,
0.48 mmol), PdACHTNUTRGNEUNG(PPh3)4 (12 mg, 0.01 mmol), NaHCO3 (1.66 g, 19.8 mmol),
H2O (9 mL) and THF (25 mL) were used. The organic layer was separat-
ed, the aqueous layer was extracted with Et2O (2ꢁ30 mL), and the com-
bined organic layers were dried over anhydrous Na2SO4 and evaporated
to dryness. Chromatography on silica gel eluting with CH2Cl2/n-hexane
(2:1) afforded Hex-TB as a white solid (0.32 g, 83%). 1H NMR (CDCl3,
400 MHz): d=7.58 (d, 4H, ArH), 7.48 (s, 2H, NH), 7.30 (d, 4H, ArH),
7.08 (s, 2H, ArH), 2.54 (t, 4H, CH2), 2.41 (t, 4H, CH2), 1.76 (m, 4H,
CH2), 1.45–1.17 (m, 48H, CH2), 0.88 (t, 6H, CH3), 0.81 ppm (t, 6H,
CH3); 13C NMR (CDCl3, 100 MHz): d=171.79, 140.21, 138.08, 137.65,
136.73, 131.03, 129.99, 119.57, 37.99, 32.73, 32.04, 31.67, 31.51, 29.75,
29.64, 29.54, 29.47, 29.35, 25.90, 22.82, 22.64, 14.25, 14.17 ppm; Anal calcd
for C54H84N2O2: C 81.76, H 10.67, N 3.53; found: C 81.43, H 10.51, N
3.73.
Terphenylene-bispropanamide (TB-1): The general procedure for Suzuki
cross-coupling was followed. 1a (0.200 g, 0.88 mmol), 1,4-phenyldiboronic
acid ester (0.087 g, 0.35 mmol), PdACHTUNGRTNEUNG(PPh3)4 (16 mg, 0.014 mmol), NaHCO3
(1.23 g, 14.6 mmol), H2O (5 mL) and THF (10 mL) were used. TB-1 was
obtained as a white solid (0.10 g, 76%). Anal calcd for C24H24N2O2: C
77.39, H 6.49, N 7.52; found: C 77.01, H 7.50, N 6.47.
AB-1: 4 (0.217 g, 0.72 mmol) and 1e (0.31 g, 0.87 mmol) were dissolved
in a solvent mixture of THF (6 mL) and diisopropylamine (4 mL) in a
Schlenk tube. The mixture was degassed and purged with nitrogen, Pd-
Terphenylene-bisnonanamide (TB-7): The general procedure for Suzuki
cross-coupling was followed. 1b (0.200 g, 0.64 mmol), 1,4-phenyldiboronic
acid ester (0.065 g, 0.26 mmol), PdACHTUNGRTNEUNG(PPh3)4 (12 mg, 0.010 mmol), NaHCO3
AHCTUNGTRENN(GUN PPh3)2Cl2 (5.1 mg, 0.0073 mmol) and CuI (2.8 mg, 0.01 mmol) were then
(0.9 g, 10.7 mmol), H2O (5 mL), and THF (10 mL) were used. TB-7 was
obtained as a white solid (0.10 g, 70%). Anal calcd for C36H48N2O2: C
79.96, H 8.95, N 5.18; found: C 79.88, H 8.99, N 5.27.
added. After the mixture was further carefully degassed and recharged
with nitrogen, it was heated to 808C and stirred for 24 h. The precipitate
was filtered and washed thoroughly with CH2Cl2, water, and THF to
afford AB-1 as a gray solid (0.13 g, 31%). Anal calcd for C38H56N2O2: C
79.67, H 9.85, N 4.89; found: C 79.40, H 9.45, N 4.90.
Terphenylene-bisdecanamide (TB-8): The general procedure for Suzuki
cross-coupling was followed. 1c (0.15 g, 0.46 mmol), 1,4-phenyldiboronic
acid ester (0.047 g, 0.19 mmol), PdACHTUNTRGNEUNG(PPh3)4 (8.8 mg, 0.0076 mmol),
AB-2: 4 (0.24 g, 0.80 mmol), PdACHTUNGTRENUNG(PPh3)2Cl2 (6 mg, 0.0085 mmol), and CuI
NaHCO3 (0.64 g, 7.6 mmol), H2O (5 mL), and THF (10 mL) were used to
afford TB-8 as a white solid (0.072 g, 66%). Anal calcd for C38H52N2O2:
C 80.24, H 9.21, N 4.92; found: C 79.80, H 9.00, N 5.06.
(55 mg, 0.289 mmol) were dissolved in pyridine (8 mL) and filled with
O2. The mixture was then stirred for 24 h. The precipitate was filtered
and washed thoroughly with CH2Cl2, water, and THF to afford AB-2 as a
gray solid (0.15 g, 63%). Anal calcd for C40H56N2O2: C, 80.49, H 9.46, N
4.69; found: C 80.22, H 9.46, N 4.62.
Terphenylene-bisundecanamide (TB-9): The general procedure for
Suzuki cross-coupling was followed. 1d (0.200 g, 0.59 mmol), 1,4-phenyl-
232
www.chemasianj.org
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2011, 6, 226 – 233

Self-assembly of coil-rod-coil molecules
TB-r-10: The general procedure for Suzuki cross-coupling was followed.
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(0.400 g, 1.08 mmol), 1,4-phenyldiboronic acid ester (0.111 g,
0.45 mmol), Pd(PPh3)4 (21 mg, 0.018 mmol), NaHCO3 (1.52 g,
G
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18.1 mmol), H2O (10 mL) and THF (30 mL) were used and afforded TB-
r-10 as a white solid (0.27 g, 92%). Anal calcd for C44H64N2O2: C 80.93,
H 9.88, N 4.29; found: C 80.56, H 9.83, N 4.27.
TB-10-E: The general procedure for Suzuki cross-coupling was followed.
6 (0.2 g, 0.56 mmol), 1,4-phenyldiboronic acid ester (0.054 g, 0.22 mmol),
PdACHTUNGTRENNUNG(PPh3)4 (5.4 mg, 0.0047 mmol), NaHCO3 (0.79 g, 9.4 mmol), H2O
(5 mL), and THF (10 mL) were used. The precipitated white solid was fil-
tered and washed with water and THF to afford TB-10-E as a white solid
(0.09 g, 65%). 1H NMR (CDCl3, 400 MHz): d=7.64 (s, 4H, ArH), 7.63
(d, 4H, ArH), 7.17 (d, 4H, ArH), 2.59 (t, 4H, CH2), 1.78 (m, 4H, CH2),
1.46–1.28 (m, 32H, CH2), 0.89 ppm (t, 6H, CH3); 13C NMR (CDCl3,
100 MHz): d=172.38, 150.32, 139.39, 138.28, 128.02, 127.49, 121.94, 34.47,
31.92, 29.62, 29.48, 29.35, 29.28, 29.14, 24.99, 22.70, 14.12 ppm. Anal calcd
for C42H58O4: C 80.47, H 9.33; found: C 80.44, H 9.30.
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Acknowledgements
Financial support by the NSF of China (Grants 20774099, 20834006, and
50821062), the 863 Program (Grant 2008AA05Z425), National Basic Re-
search Program of China (973 Program: 2009CB623601), and the Open
Project of the State Key Laboratory of Supramolecular Structure and
Materials (Grant SKLSSM200706) is gratefully acknowledged.
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