Supporting Information
Supramolecular Nanostructures from Self-Assembly
of T-Shaped Rod Building Block Oligomers
Zhuoshi Wang 1, Junjie Cui 1, Yongri Liang3, Tie Chen 1, Myongsoo Lee 2*,
Bingzhu Yin 1, and Long Yi Jin 1*
1
Key Laboratory for Organism Resources of the Changbai Mountain and Functional Molecules, Ministry of
Education, and Department of Chemistry, College of Science, Yanbian University, No. 977 Gongyuan Road, Yanji
133002, P. R. China,
2
State Key Laboratory of supramolecular Structure and Materials, Jinlin University,
Changchun 130012, P. R. China,
3
Beijing National Laboratory for Molecular Sciences, Joint Laboratory of
Polymer Science and Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
EXPERIMENTAL SECTION
1. Synthesis of the Coil Segment
Figure S1. Synthetic route of Coil Segment 9.
Synthesis of Compounds 15: To a solution of Ethyl L-(-)-lactate (36.5 g, 0.308 mol),
and 3,4-dihydro-2H-pyran (42.1 g, 0.5 mol) were slowly added 10 drops of
concentrated HCl at 0 ℃. The solution was stirred for 10 h while it reached room
temperature. Na2CO3 (3 g) was added, and stirring was continued for 10 h. The
reaction mixture was then filtered, concentrated to small volume, and distilled to give
15 (51.9 g, yield 83%).
Synthesis of Compounds 16: T o a suspension of LiAlH (12.0 g, 0.316 mol) in dry
diethyl ether (80 mL) was added a solution of 15 (51.9 g, 0.257 mol) in diethyl ether
(40 mL) at 0 ℃ under nitrogen atmosphere over 8 h. After 12 h at room temperature,
the reaction mixture was refluxed for 5 h. Methyl acetate (5 g), 10% NaOH (20 mL),
and water (80 mL) were then added in that order to the mixture cooled at room
temperature. The precipitate was filtered off, and the solution was concentrated, dried
over K2CO3 and finally distilled to give 16 (35.2 g, yield 86%).
Synthesis of Compounds 10, 12, 17: These compounds were synthesized according
to the same procedure, a representative example is described for 10. To a 250 mL
two-neck flask compound tetraethylene glycol (4.07 g，21mmol), dry THF (100 mL)
were added. After stirring for several min at 0 ℃, NaH (1g，23mmol) was added
slowly. And then iodomethane (8g，22mmol) was added dropwise for 1.5 h at 0 ℃.
The mixture was refluxed for 24 h. The reaction was concentrated by evaporation and
extracted with dichloromethane. The combined organic portions were dried over
MgSO4 and filtered. The residue was purified by flash column chromatography with
EA/CH3OH=4/1 as eluent to give product 10 (6 g, 74%) as colourless liquid.
1
H-NMR (300MHz, CDCl3, δ, ppm): 3.44-3.73 (m, 18H), 3.36 (s, 3H).
Compound 12a: 1H-NMR (300MHz, CDCl3, δ, ppm): 3.44-3.73 (m, 26H), 3.36 (s,
3H).
Compound 12b: 1H-NMR (300MHz, CDCl3, δ, ppm): 3.44-3.73 (m, 34H), 3.36 (s,
3H).
Compound 17a: 1H-NMR (300MHz, CDCl3, δ, ppm): 3.44-3.73 (m, 24H), 3.36 (s,
3H) , 1.18 (s, 3H).
Compound 17b: 1H-NMR (300MHz, CDCl3, δ, ppm): 3.44-3.73 (m, 32H), 3.36 (s,
3H) , 1.18 (s, 3H).
Synthesis of Compounds 11, 13, 18: These compounds were synthesized according
to the same procedure, a representative example is described for 11. To a 250 mL
round bottom flask Tetraethylene glycol monomethyl ether (8.24g， 40mmol),
p-Toluenesulfonyl chloride (15.3g， 80mmol)，pyridine (20ml), dry Dichloromethane
(100ml) were added. After being stirred at room temperature for 18 h, 30 mL water
was added into the reaction mixture, the aqueous phase was slowly acidified with cold
3 N HC1 to pH = 2-3 and extracted with dichloromethane (3 X 50 mL). And then the
organic fractions were dried over MgSO4. After evaporation of the solvent 12.6 g
(yield 87%) of clear oily 11 was obtained that was used without further purification.
1
H-NMR (300MHz, CDCl3, δ, ppm): 7.79 (d, J=8.2Hz, 2H), 7.33 (d, J=8.2Hz, 2H),
4.15 (t, 2H), 3.54-3.73 (m, 14H), 3.36 (s, 3H), 2.43 (s, 3H).
Compound 13a: 1H-NMR (300MHz, CDCl3, δ, ppm): 7.79 (d, J=8.2Hz, 2H), 7.33 (d,
J=8.2Hz, 2H), 4.15 (t, 2H), 3.54-3.73 (m, 26H), 3.36 (s, 3H), 2.43 (s, 3H).
Compound 13b: 1H-NMR (300MHz, CDCl3, δ, ppm): 7.79 (d, J=8.2Hz, 2H), 7.33 (d,
J=8.2Hz, 2H), 4.15 (t, 2H), 3.54-3.73 (m, 34H), 3.36 (s, 3H), 2.43 (s, 3H).
Compound 18a: 1H-NMR (300MHz, CDCl3, δ, ppm): 7.79 (d, J=8.2Hz, 2H), 7.33 (d,
J=8.2Hz, 2H), 4.15 (t, 2H), 3.54-3.73 (m, 24H), 3.36 (s, 3H), 2.43 (s, 3H), 1.18 (s,
3H).
Compound 18b: 1H-NMR (300MHz, CDCl3, δ, ppm): 7.79 (d, J=8.2Hz, 2H), 7.33 (d,
J=8.2Hz, 2H), 4.15 (t, 2H), 3.54-3.73 (m, 32H), 3.36 (s, 3H), 2.43 (s, 3H), 1.18 (s,
3H).
Synthesis of Compounds 9: These compounds were synthesized according to the
same procedure, a representative example is described for 9a. Excess K2CO3,
4-Iodophenol (0.88g, 4.02mmol), Compound 13a (1.3g, 3.2mmol) and 18-crown-6
(0.1g, 0.38mmol) were dissolved in absolute acetonitrile (50ml). The mixture was
further refluxed for 24h. the solvent was removed in a rotary evaporator and washed
by water. The mixture was extracted with ethyl acetate and dichloromethane and then
dried over anhydrous magnesium sulfate and filtered. After the solvent was removed
in a rotary evaporator, the crude product was purified by chromatography on silica gel
chromatography (EA:CH3OH=20:1 as eluent) to yield 0.85g of a yellow liquid
(62.0%). 1H-NMR (300MHz, CDCl3, δ, ppm): 7.72 (d, J=8.2Hz, 2H), 7.28 (d,
J=8.2Hz, 2H), 4.16 (t, 2H), 3.87 (t, 2H), 3.44-3.73 (m, 26H), 3.36 (s, 3H).
Compound 9b: 1H-NMR (300MHz, CDCl3, δ, ppm): 1H-NMR (300MHz, CDCl3, δ,
ppm): 7.72 (d, J=8.2Hz, 2H), 7.28 (d, J=8.2Hz, 2H), 4.16 (t, 2H), 3.87 (t, 2H),
3.44-3.73 (m, 34H), 3.36 (s, 3H).
Compound 9c: 1H-NMR (300MHz, CDCl3, δ, ppm): 1H-NMR (300MHz, CDCl3, δ,
ppm): 7.72 (d, J=8.2Hz, 2H), 7.28 (d, J=8.2Hz, 2H), 4.58-4.64 (m, 1H), 3.44-3.80 (m,
26H), 3.36 (s, 3H), 1.18 (s, 3H).
Compound 9d: 1H-NMR (300MHz, CDCl3, δ, ppm): 1H-NMR (300MHz, CDCl3, δ,
ppm): 7.72 (d, J=8.2Hz, 2H), 7.28 (d, J=8.2Hz, 2H), 4.58-4.64 (m, 1H), 3.44-3.80 (m,
34H), 3.36 (s, 3H), 1.18 (s, 3H).
2. Synthesis of rod building block
Synthesis of 3,6-Dialkyl-2,7-diiodophenanthrenequinone 4: These compounds
were synthesized according to the same procedure, a representative example is
described for 4a. To a 100 mL round bottom flask compound 3,6-Dialkylphen
anthrenequinone (1.8 g, 4.8 mmol), TFA (40 mL), and NIS (3.3 g, 14.6 mmol) were
added. After stirring for several min at RT, the reaction mixture was heated to reflux
for 3 h. The amount of solvent was reduced to 10 mL in vacuo and the mixture was
poured into ice water (100 mL), then CH2Cl2 (50 mL) was added. The organic layers
were separated and the aqueous phase was extracted with CH2Cl2 (3×). The combined
organic phase was washed with 1M Na2S2O3 solution (2×) and dried over MgSO4.
Removal of solvent in vacuo followed by flash chromatography (1:1 hexane/CH2Cl2)
gave 4a (2.64 g, 88%) as reddish orange powder. 1H-NMR (300MHz, CDCl3, δ, ppm):
8.56 (s, 2H), 7.74 (s, 2H), 2.85 (t, J = 7.8 Hz, 4H), 1.67 (p, J = 8.0 Hz, 4H), 1.25 1.38 (m, 12H), 0.92 (t, J = 7.0 Hz, 6H).
Compound 4b: 1H-NMR (300MHz, CDCl3, δ, ppm): 8.56 (s, 2H), 7.72 (s, 2H), 2.85
(t, J = 7.8 Hz, 4H), 1.67 (p, J = 8.0 Hz, 4H), 1.22 - 1.39 (m, 36H), 0.88 (t, J = 7.0 Hz,
6H).
Compound 4c: 1H-NMR (300MHz, CDCl3, δ, ppm): 8.62 (s, 2H), 7.74 (s, 2H), 2.86
(t, J = 7.8 Hz, 4H), 1.67 (p, J = 8.0 Hz, 4H), 1.21 - 1.37 (m, 60H), 0.90 (t, J = 7.0 Hz,
6H).
Synthesis of 3,6-dihexyl-2,7-diiododibenzo[a,c]phenazine 5: These compounds
were synthesized according to the same procedure, a representative example is
described for 5a. A mixture of compound 4a (2.64 g, 4.2 mmol) and
1,2-diaminobenzene (0.55 g, 5.04 mmol) in ethanol (100 mL) and acetic acid (30 mL)
was heated to reflux for 2 h. The mixture was cooled to RT and filtered. Further
washing with ethanol afforded 5a
(2.06 g, 70%) as a yellow solid. 1H-NMR
(300MHz, CDCl3, δ, ppm): 9.47(s, 2H), 8.36 (s, 2H), 8.29 (s, 2H), 7.81 (s, 2H), 2.95(t,
J = 7.6 Hz, 4H), 2.39 (s, 6H), 1.75 (p, J = 7.6 Hz, 4H), 1.25 - 1.57 (m, 12H), 0.94 (t, J
= 6.7 Hz, 6H).
Compound 5b: 1H-NMR (300MHz, CDCl3, δ, ppm): 9.46 (s, 2H), 8.35 (s, 2H), 8.29
(s, 2H), 7.81 (s, 2H), 2.95 (t, J = 7.6 Hz, 4H), 2.39 (s, 6H), 1.77 (p, J = 7.6 Hz, 4H),
1.26 - 1.57 (m, 36H), 0.92 (t, J = 6.7 Hz, 6H).
Compound 5c: 1H-NMR (300MHz, CDCl3, δ, ppm): 9.36 (s, 2H), 8.42 (s, 2H), 8.26
(s, 2H), 7.84 (s, 2H), 2.96 (t, J = 7.6 Hz, 4H), 2.38 (s, 6H), 1.73 (p, J = 7.6 Hz, 4H),
1.25 - 1.53 (m, 60H), 0.90 (t, J = 6.7 Hz, 6H).
Synthesis of 3,6-dihexyl-2,7-bis((trimethylsilyl)ethynyl)dibenzo[a,c]phenazine 6:
These compounds were synthesized according to the same procedure, a representative
example is described for 6a. Pd[P(C6H5)3]4 (0.53 g, 0.45 mmol) and CuI (0.71 g, 0.9
mmol) added to a mixture of 5a (2.06 g, 3 mmol), trimethylsilyl acetylene (4.2 mL, 30
mmol), Et3N (5 mL) and THF (30 mL). The mixture was heated to reflux for 19 h
under N2 and keep it away from the light. The mixture was then diluted with CHCl3,
washed with water (2×) and dried over MgSO4. After filtration, the filtrate was
concentrated to ca. 1.5 mL and precipitated from methanol (50 mL). The solid was
collected by filtration, and further purified by flash chromatography (4:1 and then 1:1
hexane/CH2Cl2) to give 6a (1.54 g, 80%) as a reddish orange solid. 1H-NMR
(300MHz, CDCl3, δ, ppm): 9.32 (s, 2H), 8.36 (dd, J = 6.4 Hz, 3.4 Hz, 2H), 8.29 (s,
2H), 7.81 (dd, J = 6.5 Hz, 3.4 Hz, 2H), 2.94 (t, J = 7.6 Hz, 4H), 1.77 (p, J = 7.6 Hz,
4H), 1.25 - 1.50 (m, 12H), 0.86 (t, J = 6.7 Hz, 6H), 0.39 (s, 18H).
Compound 6b: 1H-NMR (300MHz, CDCl3, δ, ppm): 9.36 (s, 2H), 8.44 (dd, J = 6.4
Hz, 3.4 Hz, 2H), 8.31 (s, 2H), 7.81 (dd, J = 6.5 Hz, 3.4 Hz, 2H), 2.96 (t, J = 7.6 Hz,
4H), 1.77 (p, J = 7.6 Hz, 4H), 1.25 - 1.48 (m, 36H), 0.88 (t, J = 6.7 Hz, 6H), 0.39 (s,
18H).
Compound 6c: 1H-NMR (300MHz, CDCl3, δ, ppm): 9.32 (s, 2H), 8.36 (dd, J = 6.4
Hz, 3.4 Hz, 2H), 8.29 (s, 2H), 7.81 (dd, J = 6.5 Hz, 3.4 Hz, 2H), 2.94 (t, J = 7.6 Hz,
4H), 1.77 (p, J = 7.6 Hz, 4H), 1.25 - 1.50 (m, 60H), 0.88 (t, J = 6.7 Hz, 6H), 0.32 (s,
18H).
Synthesis of 2,7-diethynyl-3,6-dihexyldibenzo[a,c]phenazine 7: These compounds
were synthesized according to the same procedure, a representative example is
described for 7a. A solution of
6a (1.54 g, 2.4 mmol) and K2CO3 (2 g, 14.4mmol) in
THF/MeOH (30 mL/30 mL) was stirred at room temperature for 3 h. The reaction
was concentrated by evaporation and extracted with dichloromethane. The combined
organic portions were dried over MgSO4 and filtered. The residue was purified by
flash column chromatography with 30% CH2Cl2 in hexanes to give product 7a (1.08 g,
91%) as yellow solid. 1H-NMR (300MHz, CDCl3, δ, ppm): 9.32 (s, 2H), 8.36 (dd, J =
6.4 Hz, 3.4 Hz, 2H), 8.29 (s, 2H), 7.81 (dd, J = 6.5 Hz, 3.4 Hz, 2H), 3.44 (s, 2H), 2.94
(t, J = 7.6 Hz, 4H), 1.77 (p, J = 7.6 Hz, 4H), 1.25 - 1.50 (m, 12H), 0.86 (t, J = 6.7 Hz,
6H).
Compound 7b: 1H-NMR (300MHz, CDCl3, δ, ppm): 9.36 (s, 2H), 8.44 (dd, J = 6.4
Hz, 3.4 Hz, 2H), 8.31 (s, 2H), 7.81 (dd, J = 6.5 Hz, 3.4 Hz, 2H), 3.44 (s, 2H), 2.96 (t,
J = 7.6 Hz, 4H), 1.77 (p, J = 7.6 Hz, 4H), 1.25 - 1.48 (m, 36H), 0.88 (t, J = 6.7 Hz,
6H).
Compound 7c: 1H-NMR (300MHz, CDCl3, δ, ppm): 9.32 (s, 2H), 8.36 (dd, J = 6.4
Hz, 3.4 Hz, 2H), 8.29 (s, 2H), 7.81 (dd, J = 6.5 Hz, 3.4 Hz, 2H), 3.52 (s, 2H), 2.94 (t,
J = 7.6 Hz, 4H), 1.77 (p, J = 7.6 Hz, 4H), 1.25 - 1.54 (m, 60H), 0.86 (t, J = 6.7 Hz,
6H).
Figure S2. 1H-NMR spectra of molecules 1a, 2a, 3a in CDCl3
Figure S3. MALDI-TOF-Mass spectrum of 1, 2, 3 (matrix: CHCA)
Table S1. Indexed small-angle X-ray diffraction peaks
for the hexagonal perforated layer phase (HPL) in
compounds 2a at 40 oC.
Figure S4. Small-angle X-ray diffraction patterns of 2a plotted against q (=4πsinθ/λ) measured at
various temperature. (a) at 25 oC, (b) at 80 oC,(c) at 135 oC, (d) at 160 oC, (e) at 140 oC, (f) at 40
oC.
Figure S5
Figure S6.
Figure S5. Small-angle X-ray diffraction patterns of 1b plotted against q (=4πsinθ/λ) in different
temperature. (a) at 25 oC, (b) at 80 oC,(c) at 130 oC, (d) at 70 oC.
Figure S6. Small-angle X-ray diffraction patterns of 2c plotted against q (=4πsinθ/λ) in different
temperature. (a) at 25 oC, (b) at 48oC,(c) at 85oC, (d) at 65 oC, (e) at 40 oC.
Table S2. Small-Angle X-ray Diffraction Data for the rectangular columnar
structure of 1b and oblique columnar structure of 2c 25 oC.
Table S3. Small-Angle X-ray Diffraction Data for the
Body-Centered Tetragonal Structure of 3a measured at
25 ℃.
Figure S7. Small-angle X-ray diffraction patterns of 3a plotted against q (=4πsinθ/λ) in different
temperature. (a) at 25 oC, (b) at 45 oC,(c) at 85 oC, (d) at 50 oC.