Supporting Information
Ordered Nanostructures from Self-Assembly of Rod-Coil Oligomers
with n-shaped Rod and Dendritic Poly(Ethylene Oxide) Coil Segment
Ke-li Zhongb, Zhuoshi Wanga†, Yongri Liangc, Tie Chena*, Bingzhu Yina and Long Yi Jina*
a. Key Laboratory for Organism Resources of the Changbai Mountain and Functional
Molecules(Yanbian University), Ministry of Education, and Department of Chemistry, College
of Science, Yanbian University, Yanji, Jilin, 133002, China;
b. College of Chemistry, Chemical Engineering and Food Safety, Bohai University. Food
Science Research Institute of Bohai University, Food Safety Key Lab of Liaoning Province,
Jinzhou, Liaoning, 121013, China;
c. Beijing National Laboratory for Molecular Sciences, Joint Laboratory of Polymer Science
and Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
1
Techniques
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H-NMR spectra were recorded from CDCl3 solutions on a Bruker AM 300 spectrometer.
The purity of the products was checked by column chromatography (silica gel 100-200). A
Perkin Elmer Pyris Diamond differential scanning calorimeter was used to determine the
thermal transitions, which were reported as the maxima and minima of their endothermic or
exothermic peaks, the heating and cooling rates were controlled to 10 ℃/min. X-ray scattering
measurements were performed in transmission mode with synchrotron radiation at the 3C2
X-ray beam line at Pohang Accelerator Laboratory, Korea. MALDI-TOF-MS was performed on
a perceptive Biosystems Voyager-DE STR using a 2-cyano-3-(4-hydroxyphenyl) acrylic acid
(CHCA) as matrix. The UV/Vis and the fluorescence spectra were obtained from a Shimadzu
UV-1650PC spectrometer and a Hitachi F-4500 fluorescence spectrometer, respectively. DLS
measurements were performed by using a UNIPHASE He–Ne laser operating at 632.8 nm. The
scattering was kept at 908 during the whole experiment. The maximum operating power of the
laser was 30 mW. The detector optics employed optical fibers coupled to an
ALV/SOSIPD/DUAL detection unit, which employed an EMI PM-28B power supply and
ALV/PM-PD preamplifier /discriminator. The signal analyzer was an ALV5000/E/WIN
multiple-tau digital correlator with 288 exponentially spaced channels. The hydrodynamic
radius (RH) was determined from the DLS autocorrelation functions by the cumulants and the
CONTIN methods by using the software provided by the manufacturer. The transmission
electron microscope (TEM) was performed at 120kV using JEOL 1020. Sample was stained by
depositing a drop of 2 wt % uranyl acetate aqueous solution onto the surface of the
sample-loaded grid and dried at 45 oC.
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Synthesis
Scheme S1. Synthetic routes of compound 6a, 6b, 6c.
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Synthesis of compound 3a，5a
Compounds 3a, 5a were synthesized by the same procedure. A representative example is
described for 3a. Compounds 2a (15.21g, 40mmol), dry CH2Cl2 (100mL), pyridine (30mL) and
toluene-p-sulfonyl chloride (TsCl, 15.3g, 80mmol) was put into one-neck flask. The mixture
was stirred for 6h at room temperature, and then water (50mL) was added and further stirred for
2h. The diluted hydrochloric acid was added and acidified to PH<7. The resulting solution was
extracted with methylene chloride and the organic solution was dried (MgSO4) and filtered.
After the solvent was removed in a rotary evaporator, the crude product was purified by silica
gel chromatography to yield colorless liquid (87%). 1H NMR(250MHz, CDCl3, δ, ppm): 7.79(d,
2ArH, o to SO3, J=8.2Hz), 7.33(d, 2ArH, o to CH3, J=8.2Hz), 4.15(t, 2H, OCH2CH2OSO2),
3.44-3.73(m, 30H for 3a, 46H for 5a , -OCH2CH2O- and OCH2CH2OSO2), 3.36(s, 3H, OCH3),
2.43(s, 3H, CH3phenyl).
Synthesis of compound 2a，4a
Compounds 2a, 4a were synthesized by the same procedure. A representative example is
described for 4a. Tetraethylene glycol (4.07g, 21mmol), dry THF (100mL) was put into
one-neck flask. NaH (1g, 23mmol) was added with small portions at 0oC and then 3a (11.92g,
22mmol) in THF (30mL) was added by dropwise for 1.5h, the mixture was refluxed for 24h.
The solvent was removed and washed by water and extracted with methylene chloride and the
organic solution was dried (MgSO4) and filtered. After the solvent was removed in a rotary
evaporator, the crude product was purified by silica gel chromatography (EA/CH3OH=4/1 as
eluent) to yield colorless liquid (74%). 1H NMR (250MHz, CDCl3, δ, ppm): 3.44-3.73(m, 32H
for 2a, 48H for 4a, -OCH2CH2O-), 3.36(s, 3H, OCH3).
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Synthesis of compound 6a
5a (2.86g, 4mmol), dry acetonitrile (100mL), K2CO3 (2.76g, 20mmol) 4-hydroxyl-4'iodobiphenyl (1.3g, 4.4mmol) was put into flask. The mixture was refluxed for 20h, and then
the solvent was removed and washed by water and extracted with dichlormethane and the
organic solution was dried (MgSO4) and filtered. After the solvent was removed in a rotary
evaporator, the crude product was purified by silica gel chromatography (EA/CH3OH=5/1 as
eluent) to yield 2.63g of colorless liquid (78%). 1H NMR(250MHz, CDCl3, δ, ppm): 7.72(d,
2ArH, o to I, J=8.2Hz), 7.47(d, 2ArH, m to I, J=8.2Hz), 7.28(d, 2ArH, m to phOCH2, J=8.2Hz),
6.97(d, 2ArH, o to phOCH2, J=8.2Hz), 4.16(t, 2H, OCH2CH2Oph), 3.87(t, 2H, OCH2CH2Oph),
3.44-3.73(m, 44H, -OCH2CH2O-), 3.36(s, 3H, OCH3).
Synthesis of compound 2b
Tetraethylene glycol (3.88g, 20mmol), dry THF (100mL) was put into one-neck flask. NaH
(0.96g, 22mmol) was added with small portions at 0oC and then 2-methoxyethyl
4-methylbenzenesulfonate (4.84g, 21mmol) in THF (30mL) was added by dropwise for 1h, the
mixture was refluxed for 20h. The solvent was removed and washed by water and extracted
with methylene chloride and the organic solution was dried (MgSO4) and filtered. After the
solvent was removed in a rotary evaporator, the crude product was purified by silica gel
chromatography (EA/CH3OH=5/1 as eluent) to yield 3.8g of colorless liquid (75%). 1H NMR
(250MHz, CDCl3, δ, ppm): 3.44-3.73(m, 20H, -OCH2CH2O-), 3.36(s, 3H, OCH3).
Synthesis of compound 3b
Dry NaH (0.63g, 26.1mmol), compound 2b (4.6g, 18.3mmol) and freshly distilled dry THF
(100mL) were placed in a dry round bottomed flask under N2. Methallyl dichloride (1.1g, 8.7
mmol) was added dropwise at room temperature. The mixture was stirred at room temperature
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for 30min and then refluxed for 18h. After cooling to room temperature, the reaction mixture
was quenched by water (5mL) and the THF was removed in a rotary evaporator. The crude
mixture was washed with water, extracted with methylene chloride, dried (MgSO4) and filtered.
The crude product could be separated by column chromatography (silica gel) with CH2Cl2 as
eluent. Yield: 2.87 g (60%). 1H NMR (250MHz, CDCl3, δ, ppm): 5.10(s, 2H, CH2=), 4.01(s, 4H,
CH2=C-CH2O), 3.46-3.76(m, 40H, -OCH2CH2O-), 3.37(s, 6H, OCH3).
Synthesis of compound 4b
Freshly distilled dry THF (50mL) and compound 3b (3.02g, 5.4mmol) were placed in a dry
round bottomed flask under N2 and cooled to 0 oC in ice bath. A solution of BH3 (1M) in THF
(11mL) was added slowly to this mixture, which was then stirred at 0 oC for 2h. The reaction
mixture was quenched with a solution of NaOH in water (3M, 5mL) and allowed to stir for 15
min. This was followed by addition of H2O2 aqueous solution (30%, 5mL) and the mixture was
stirred at room temperature for 30min. The reaction mixture was saturated with K2CO3 and
extracted with diethyl ether. The organic layer was dried over anhydrous MgSO4, the solvent
was removed in a rotary evaporator, and the crude product was purified by column
chromatography(silica gel) with CH2Cl2/MeOH=5/1 as eluent to afford 1.1g colorless
liquid(35%).
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H NMR(250MHz, CDCl3, δ, ppm): 3.26-3.83(m, 46H, HOCH2CHCH2O,
-OCH2CH2O-), 3.14(s, 6H, OCH3), 1.87(m, 1H, HOCH2CHCH2O).
Synthesis of compound 5b
Compound 5b were synthesized according to the same procedure with compound 1a.
Compound 5b: Yield: 50%. 1H NMR(250MHz, CDCl3, δ, ppm): 7.78(d, 2ArH, o to SO3,
J=8.2Hz), 7.34(d, 2ArH, o to CH3, J=8.2Hz), 4.11(d, 2H, CHCH2OSO2), 3.40-3.65(m, 44H,
-OCH2CH2OCH2CH), 3.37(s, 6H, OCH3), 2.44 (s, 3H, CH3phenyl), 2.24(m, 1H, CH).
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Synthesis of compound 6b
Compound 6b were synthesized according to the same procedure with compounds 6a.
Compound 6b: Yield: 78%. 1H NMR(250MHz, CDCl3, δ, ppm): 7.72(d, 2ArH, o to I, J=8.2Hz),
7.47(d, 2ArH, m to I, J=8.2Hz), 7.28(d, 2ArH, m to phOCH2, J=8.2Hz), 6.97(d, 2ArH, o to
phOCH2, J=8.2Hz), 4.09(d, 2H, OCH2CH2Oph), 3.52-3.63(m, 44H, -OCH2CH2OCH2CH),
3.37(s, 6H, OCH3), 2.42(m, 1H, CH).
Synthesis of compound 2c-6c
These Compounds were synthesized according to the same procedure with compounds 2b-6b.
Compound 2c: Yield: 80%. 1H NMR (250MHz, CDCl3, δ, ppm): 5.18(s, 2H, CH2=), 4.02(s, 4H,
CH2=C-CH2O), 3.54-3.67(m, 16H, -OCH2CH2O-), 3.37(s, 6H, OCH3).
Compound 3c: Yield: 50%. 1H NMR (250MHz, CDCl3, δ, ppm): 3.73(d, 2H, HOCH2CH),
3.50-3.64(m, 20H, HOCH2CHCH2OCH2CH2O-), 3.36(s, 6H, OCH3), 2.14(m, 1H, CH).
Compound 4c: Yield: 86%. 1H NMR (250MHz, CDCl3, δ, ppm): 5.16(s, 2H, CH2=), 4.08(s, 4H,
CH2=C-CH2O), 3.37-3.65(m, 44H, -OCH2CH2O-), 3.37(s, 12H, OCH3).
Compound 5c: Yield: 80%. 1H NMR (250MHz, CDCl3, δ, ppm): 3.46-3.65(m, 50H, -CH2O-),
3.37(s, 12H, OCH3), 2.08-2.19(m, 3H, CH).
Compound 6c: Yield: 68%. 1H NMR (250MHz, CDCl3, δ, ppm): 7.71(d, 2ArH, o to I,
J=8.2Hz), 7.46(d, 2ArH, m to I, J=8.2Hz), 7.27(d, 2ArH, m to phOCH2, J=8.2Hz), 6.96(d,
2ArH, o to phOCH2, J=8.2Hz), 4.03(d, 2H, CH2Oph), 3.45-3.63(m, 48H, -CH2O-), 3.37(s, 12H,
OCH3), 2.15-2.38(m, 3H, CH).
Synthesis of 1,8-diiodoanthraquinone (2) (see references S1-S3)
A mixture of 1, 8-dichloroanthraquinone (25.0g, 90.2mmol), Cu powder (2.01g, 31.5 mmol),
and NaI (50.0 g, 334 mmol) in PhNO2 (110 mL) was heated under reflux for 43 h. The solvent
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was removed by steam distillation, and H2O was removed by decantation followed by
evaporation. The solid was dissolved in a minimum amount of boiling chlorobenzene (ca. 1.0
L), and the insoluble materials were removed by filtration while hot. The filtrate was allowed to
stand for 3d and the formed brown crystals were collected by filtration. The yield was 16.7 g
(40%); 1H NMR (300 MHz, CDCl3, δ, ppm): 8.40 (dd, 2 H, 4, 5-anthracene-H, J = 1.4, 7.7 Hz),
8.28 (dd, 2 H, 2,7-anthracene-H, J =1.4 ,7.7 Hz), 7.35 (t, 2 H, 3,6-anthracene-H, J = 7.7 Hz,).
Anal. Calcd for C14H8I2O: C, 37.70; H, 1.81. Found: C, 37.66; H, 1.83.
Synthesis of 1, 8-Diiodoanthracene (3) (see references S1-S3)
To a stirred suspension of 4, 5-diiodo-9-anthrone (2.00g, 4.48mmol) in n-PrOH (90mL),
NaBH4 (0.847g, 22.4mmol) was added with small portions over 30min. The mixture was
further stirred for 1 h at room temperature to give a clear orange solution. After addition of conc.
HCl (12mL), the mixture was refluxed for 1h. The formed solid was collected by filtration,
washed with H2O and air-dried. The solid was separated by chromatography on silica gel
(hexane/CH2Cl2= 5/1) and recrystallized from EtOH to give 1.72g of the yellow crystals (89%).
1
H NMR(250MHz, CDCl3, δ, ppm): 8.96(s, 1H, 9-anthracene-H), 8.33 (s, 1H, 10-anthracene-H),
8.16 (d, 2H, 4,5-anthracene-H, J=6.9 Hz), 8.02 (d, 2H, 2,7-anthracene-H, J=8.5Hz), 7.21 (dd,
2H, 3,6-anthracene-H, J=6.9, 8.5 Hz). Anal. Calcd for C14H8I2: C, 39.10; H, 1.88. Found: C,
39.16; H, 1.85.
Synthesis of 1,8-diethynylanthracene (5) (see references S1-S3)
1, 8-di (3-methyl-3-hydroxy-1-butynyl) anthracene (286mg, 0.84mmol), NaOH (0.36g, 8.4
mmol) were dissolved in toluene (30mL). The mixture was refluxed for 2h, and then the solvent
was removed and washed by water. The mixture was extracted with ethyl acetate and dried over
anhydrous magnesium sulfate and filtered. After the solvent was removed in a rotary evaporator,
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the crude product was purified by chromatography on silica gel (PE as eluent) to yield 158mg
of a yellow solid (83%). 1H NMR (250MHz, CDCl3, δ, ppm): 9.44 (s, 1H, 9-anthracene-H),
8.46 (s, 1H, 10-anthracene-H), 8.03 (d, 2H, 4,5-anthracene-H, J=8.6 Hz), 7.79 (d, 2H,
2,7-anthracene-H, J=6.9 Hz), 7.44 (dd, 2H, 3,6-anthracene-H, J=6.9, 8.6 Hz), 3.62 (s,
2H,C≡C-H). Anal. Calcd for C18H10: C, 95.55; H, 4.45. Found: C, 95.61; H, 4.41.
Figure S1. 1H-NMR of the representative molecules 1a-1c (solvent: CDCl3).
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Figure S2. DSC traces (10 oC / min) recorded during the second heating scan and the second
cooling scan of 1a.
Figure S3. Absorption and emission spectra of 1b for (a) and 1c for (b) in CHCl3 and aqueous
solution (0.002 wt %), autocorrelation functions of 1b for (c) and 1c for (d) in aqueous solution
(0.01 wt%),
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Figure S4. Angular dependence of diffusion coefficient for 1a-1c.
The molecular numbers on the cross-sectional area of the per cylindrical micelle
The fiber diameters obtained from TEM image are R1a=9.8nm，R1b=8.0nm，R1c=6.5nm
respectively, accordingly the cross-sectional area of cylindrical micelle are Area1a=π*(R/2)2
=75.39nm2，A1b=50.24nm2，A1c=33.17 nm2 . The width of rod core is 1.0nm from CPK
modeling. The fully stretched lengths of molecule are L1a=5.6nm，L1b=4.1nm，L1c=3.0nm.
Ignoring the volume occupied by the stretching flexible chain, the areas of each molecule
calculated based on rectangle are S1a=W*L =5.6nm2，S1b=4.1nm2，S1c=3.0nm2. Thus the largest
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molecular numbers on the cross-sectional area of the per cylindrical micelle is n1a= A/S =13.5，
n1b=12.2，n1c=11.0. However, actually when the length is fixed, with the increase of the flexible
chain branches, the molecules become wider, therefore the areas of individual molecule become
larger and the molecular numbers in the per cylindrical micelle become less.
Figure S5. The fully stretched molecular lengths of 1a, 1b, 1c by CPK modeling.
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Katz, H. The Journal of Organic Chemistry. 1989, 54, 2179.
[S2]
Toyota, S.; Suzuki, S.; Goichi, M. Chemistry-A European Journal. 2006, 12, 2482.
[S3]
Bar, A. K.; Gole, B.; Ghosh, S.; Mukherjee, P. S. Dalton Transactions. 2009, 6701.
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