A facile synthesis and properties of multicarbazole molecules containing multiple vinylene bridges

Article abstract of DOI:10.1021/ja043510s

Multibranched π-conjugated materials and hyperbranched polymers have received considerable interest in both academic research and industrial applications because of their unusual molecular structures and properties. In this communication, we provide an efficient approach to synthesize two novel π-conjugated multibranch compounds, which have good solubility and are nanosize (about 5 nm). The double bonds of the multibranch compounds are synthesized using solvent-free Wittig-Horner-Emmons reactions. The reaction conditions are simple and mild. Their optical properties are discussed too. Copyright

Full text of DOI:10.1021/ja043510s

Supporting Information for
A Facile Synthesis and Properties of Multi-carbazole Molecules Containing
Multiple Vinylene Bridges
Jia-Xiang Yang, Xu-Tang Tao*, Chun Xue Yuan, Yun Xing Yan, Lei Wang, Zhi Liu, Yan Ren,
Ming Hua Jiang
State Key Laboratory of Crystal Materials, Shandong University, Jinan, 250100, P. R. China
E-mail: txt@icm.sdu.edu.cn.
General Methods. Chemicals were purchased from Aldrich, Acros and used as received. 1HNMR
and 13CNMR spectra were recorded at 25°C using Bruker Avance 400 or 600 spectrometer.
Coupling constants J are given in Hertz. Microanalyses (C, H, N) were performed using a German
Vario EL III elemental analyzer. IR spectra were obtained on a Nicolet NEXUS 670 spectrometer
(KBr pellets). Electrospray mass spectrum (ES-MS) was recorded on a Finnigan LCQ mass
spectrograph, and the concentration of the samples was about 1.0 mmol/mL. The diluted solution
was electrosprayed at a flow rate of 5×10-6 L/min with a needle voltage of 4.5 kV. The mobile
phase was an aqueous solution of methanol (V/V, 1:1). The experiments were performed using a
Bruker Biflex III matrix assisted laser desorption/ionization time of flight (MALDI-TOF) mass
spectrometer equipped with a 337 nm nitrogen laser. Both matrice 4-hydroxy-α-cyanocinnamic
acid and sample were dissolved in 1:1 (v/v) acetonitrile : water with 1% trifuoroacetic acid. And
0.5 µl of this mixture solution was placed on a metal sample plate and air-dried at ambient
temperature. Mass spectra were acquired in positive linear mode and using an acceleration voltage
of 19 kV. External mass calibration was performed using a standard peptide mixture. Spectra were
obtained by setting the laser power close to the thresold of ionization and generally 100 pulses
were acquired and averaged. Mass spectrum was determined with a Micromass GCT-MS (EI
source). Absorption spectra were recorded on
a
UV-265 spectrophotometer. The
photoluminescence spectra were collected on a Perkin Elmer LS55 spectrofluorimeter. Solvents
were purified and dried according to standard procedures.
S 1

Scheme 1
COCH3
CH3CH2CH2CH2Br
(CH3CO)2O
AlCl3
(C4H9)4NBr
NaOH
N
H
N
2
N
1
3
CHO
N
N
POCl3
DMF
SiCl4
N
N
N
N
4
5
CHO
CHO
N
N
+
+
OHC
OHC
N
N
N
N
6
7
CHO
S 2

Scheme 2
NaOH
9
aq. NaOH
COCH3
+
CHO
O
O
8
9
O
11
PO(OCH3)2
10
NH4Ac
a NBS
b P(OCH3)3
CH3CH2OH
N
N
(H3CO)2OP
13
PO(OCH3)2
12
N
N
N
N
5 + 13
N
N
N
N
N
N
G0
S 3

Scheme 3
a. NaOH
b. NH4Ac
OHC
CHO
COCH3
+
N
N
14
9
15
(H3CO)2OP
PO(OCH3)2
a. NBS
N
N
b. P(OCH3)3
(H3CO)2OP
PO(OCH3)2
16
N
N
N
N
N
N
N
N
5
+ 16
N
N
N
N
N
N
G1
S 4

Experimental Section
N-(n-butyl)-carbazole 2. To a stirring of carbazole 1 (16.7 g, 100 mmol), Bu4NBr (0.15 g) and
NaOH (6.4 g, 160 mmol) in CH3COCH3 (100 mL) was added 1-bromobutane (10 mL) and
refluxed. After refluxing for 24 h, the solvents were removed under reduced pressure, and 200 mL
water was added to the flask and white solid formed. The white solid was collected by filtration
and washed with water. The solid was recrystallized from mixture ethanol and water and gave
white needle crystals. Yield: 18.1 g, 81.2%. mp 58.65-62.11 °C.
IR (cm-1): 3043, 2972, 2953, 2929, 2869, 2858, 1625, 1592, 1483, and 1378.
1HNMR(CDCl3, 400MHz, ppm) δ: 0.95 (t, 3 H, J = 7.54), 1.39 ( m, 2 H), 1.86 ( m, 2 H), 4.31 (t, 2
H, J = 7.20), 7.19-7.48 (m, 6 H), 8.00 (d, 2 H, J = 8.54).
3-acetyl-9-(n-butyl)-carbazole 3. To a stirring of N-(n-butyl)-carbazole 2 (4.46 g, 20 mmol) in
anhydrous methylene dichloride (80 mL) was added immediately anhydrous AlCl3 (5.2 g, 40
mmol), yielding a black suspension. The mixture was cooled to 0 °C under ice bath. Acetic
anhydride (2.04 g, 20 mmol) dissolved methylene dichloride (20 mL) was slowly added dropwise
via syringe under vigorous stirring. On completion of the addition, the ice bath was removed, and
the dark green slurry solution was warm to room temperature with stirring over night. The mixture
was poured into a mixture of ice and concentrated HCl, extracted three times with CH2Cl2, washed
with 1M Na2CO3 solutions and saturated brine consequently, and the extracts was separated, dried
over MgSO4. After removing solvents under reduced pressure, the residue was purified by flash
chromatography on silica gel using petroleum/ethyl acetate (4:1) as elutent, and gave
3-acetyl-9-(n-butyl)-carbazole as slurry. Yield: 4.01 g, 75.1%. mp 58.44-62.11 °C.
IR (cm-1): 3045, 3002, 2958, 2925, 2875, 2861, 1663, 1623, 1591, 1494, 1466, and 1380. A
strong peek at 1663 cm-1 is the νs of C=O moiety
1HNMR (CDCl3, 600MHz, ppm) δ 0.98 (t, 3H, J = 7.40), 1.43 (m, 2H), 1.89 (m, 2H), 2.74 (s, 3H),
4.34 (t, 2H, J = 7.25), 7.32 (t, 1H), 7.42 (d, 1 H, J = 8.6), 7.45 (d, 1 H, J = 8.2), 7.53 (t, 1 H), 8.14
(dd, J = 8.6; 1.6), 8.17 (d, 1 H, J = 7.7), 8.76 (d, 1 H, J = 1.6).
13CNMR (CDCl3, 150.90MHz, ppm) δ: 13.84, 20.57, 26.59, 31.15, 43.21, 108.36, 109.32, 120.05,
120.70, 121.92, 122.80, 123.38, 126.48, 126.50, 129.04, 141.33, 143.36, 197.51.
1,3,5-tri(N-(n-butyl)-3-carbazolyl)benzene 4. 3-acetyl-9-(n-butyl)-carbazole 3 (2.67 g, 10
mmol) was dissolved in ethanol. Tetrachlorosilane(10 mL) was slowly added with dropwise to the
solution under vigorous stirring at 0 °C. After complete addition, the reaction mixture was warmed
to room temperature. Stirring continued under nitrogen for 24 h. This mixture was poured in water
and extracted with CH2Cl2 three times. The organic layer was washed with water and saturated
brine consequently. The organic extracts were dried over MgSO4. After removed solvents under
reduced pressure, the residue was purified by flash column chromatography with light petroleum-
methylene dichloride (2:1) as the eluent, and gave the product as light yellow solid. Yield: 0.74 g,
S 5

30%, mp 207°C.
IR (cm-1): 3047, 2596, 2929, 2872, 1598, 1491, 1470, 1381, 872, 810, and 746.
MALDI-TOF, m/z: cal.: 741.4, found: 741.5. Shown in Figure S1.
Anal. Cal. For C54H51N3: C, 87.41; H, 6.93; N, 5.66. Found: C, 87.15; H, 6.88; N, 5.61 %.
1HNMR (CDCl3, 600MHz, ppm) δ: 1.01 (t, 9H, J = 7.40), 1.49 (m, 6H), 1.95 (m, 6H), 4.40 (t, 6H,
J = 7.14), 7.28 (m, 3 H), 7.47 (d, 3 H, J = 8.15), 7.52 (m, 3 H), 7.56 (d, 3 H, J = 8.43), 7.94 (dd,
3H, J = 8.43; 1.72), 8.05 (s, 3H), 8.21(d, 3H, J = 7.68), 8.53 (d, 3H, J = 1.62).
13CNMR (CDCl3, 150.90MHz, ppm) δ: 13.91, 20.62, 31.21, 43.02, 108.83, 108.96, 118.92, 119.19,
120.54, 123.07, 123.44, 124.80, 125.45, 125.78, 132.68, 140.12, 140.98, 143.24.
Compound 5, 6 and 7. POCl3 (0.92 mL, 10 mmol) was slowly dropped into a dry 100 mL flask,
which contained DMF (0.74 mL, 10 mmol) and has been cooled with ice water bath in advance.
The mixture was stirring while POCl3 was dropping. A whole white solid bulk appeared in the
flask soon end of dropping. 4 (741 mg, 1 mmol) that was dissolved in 30 mL ClCH2CH2Cl was
added the flask, then ice water bath was removed. After the white solid bulk disappeared under r.t.,
the reaction mixture was stirred and refluxed for about 16 h. the ClCH2CH2Cl was evaporated out
after completion of the reaction (exhaution of 4 could be observed by TLC). The remains were
poured into 100 mL ice water. NaHCO3 was added to modify the PH under vigorously stirring.
After the PH at 8, continuously stirring was kept for about 1 h. the suspension was extracted with
CH2Cl2 and washed with water and brine. The organic extracts were dried over MgSO4. After
removing the solvents under reduced pressure. The residue was purified by flash chromatography
with light petroleum/ethyl acetate (4:1) as elutent, and gave the compound 5, compound 6 and
compound 7 as yellow solid. Yield: 5 100 mg, 13 %; 6 220 mg, 27.6%; 7 300 mg, 36.3%.
Spectroscopic and analytical data for compound 5
IR (cm-1): 3049.0, 2957.1, 2871.5, 1684.9, 1596.1, 1490.4, 1382.7, 871.7, 804.4, and 747.2.
Compared with 4, 2871.5 cm-1, 2730.8 cm-1 are C-H characteristic absorption of formyl, and a
strong peek at 1684.9 cm-1 is the νs of C=O moiety.
1HNMR (CDCl3, 400MHz, ppm) δ: 1.00 (m, 9 H), 1.46 (m, 6 H), 1.93 (m, 6 H), 4.40 (m, 6 H),
7.25-8.05 (overlapping multiples, 17 H), 8.20 (d, 2 H, J = 7.72), 8.50 (d, 2 H, J = 1.56), 8.58 (d, 1
H, J =1.56), 8.72 (d, 1 H, J = 1.36), 10.12 (s, 1 H).
13CNMR (100.61 MHz, CDCl3) δ: 13.42, 20.11, 30.73, 42.6, 108.37, 108.51, 108.69, 109.23,
118.47, 118.68, 119.01, 120.06, 122.55, 122.80, 122.97, 123.15, 123.91, 124.23, 124.68, 124.94,
125.34, 126.04, 126.63, 128.22, 132.01, 133.80, 139.67, 140.29, 140.50, 142.11, 142.92, 144.06,
191.23.
Spectroscopic and analytical data for compound 6
IR (cm-1): 3049.0, 2957.0, 2928.9, 2871.5, 2734.6, 1685.2, 1628.7, 1596.1, 1489.5, 1382.7,
871.7, 804.7, and 747.2. Compared with 4, 2871.5 cm-1, 2734.6 cm-1 are C-H characteristic
absorption of formyl, and a strong peek at 1685.2 cm-1 is the νs of C=O moiety.
S 6

1HNMR (CDCl3, 600MHz, ppm) δ: 1.02 (m, 9 H), 1.48 (m, 6 H), 1.96 (m, 6 H), 4.41 (m, 6 H),
7.30 (m, 1 H), 7.47 (d, 1 H, J = 8.70), 7.52 (d, 1 H, J = 7.39), 7.55 (d, 2H, J = 8.52), 7.57 (d, 1 H,
J = 8.44), 7.62 (d, 2 H, J = 8.44), 7.95 (dd, 1 H, J = 8.52; 1.51), 8.00-8.10 (overlapping multiples,
7 H), 8.24 (d, 1 H, J = 7.67), 8.53 (s, 1 H), 8.61 (s, 2 H), 8.75 (s, 2 H), 10.14 (s, 2 H).
13CNMR (CDCl3, 150.92 MHz, ppm) δ 13.90, 14.19, 20.56, 20.61, 31.15, 31.26, 43.03, 43.41,
108.88, 109.03, 109.19, 109.75, 118.98, 119.14, 119.49, 120.55, 123.01, 123.48, 123.66, 124.29,
124.66, 125.09, 125.40, 125.87, 126.51, 127.22, 128.72, 132.31, 134.11,140.20, 140.83, 140.99,
142.76, 143.58, 144.56, 191.70.
Spectroscopic and analytical data for compound 7
IR (cm-1): 3049.0, 2957.5, 2928.9, 2871.5, 2734.6, 1684.8, 1628.4, 1595.8, 1485.9, 1382.7,
871.7, and 806.3. Compared with 4, 2871.5 cm-1, 2734.6 cm-1 are C-H characteristic absorption of
formyl, and a strong peek at 1684.8 cm-1 is the νs of C=O moiety.
1HNMR (CDCl3, 600MHz, ppm) δ: 1.02 (t, 9 H, J = 7.30), 1.48 (m, 6H), 1.97 (m, 6 H), 4.43 (t, 6
H, J = 6.90), 7.54 (d, 3 H, J = 8.45), 7.62 (d, 3 H, J = 8.39), 8.01 (d, 3 H, J = 8.39), 8.06 (d, 6 H),
8.59 (s, 3 H), 8.74 (s, 3 H), 10.15 (s, 3H).
13CNMR (CDCl3, 150.92 MHz, ppm) δ: 13.41, 20.11, 21.07, 30.70, 42.96, 108.75, 109.35, 119.01,
122.81, 123.23, 123.75, 124.56, 126.05, 126.86, 128.29, 133.47, 140.44, 142.47, 144.12, 191.24.
1, 3-Di-p-tolyl-propenone 10. A flask was charged with a mixture p-toluadehyde 8 (6 g, 50
mmol), 4-methylacetophenone 9 (6.8 g, 51 mmol) and 2 % aqueous sodium hydroxide (150 mL)
was vigorously stirred at room temperature for 30 min, and then was heated about 60 °C for 6 h.
The reaction was monitored by TLC. After the reaction was completed, cooled to room
temperature, a light yellow solid precipitated that was filtered, washed thoroughly with water,
air-dried to give 11.6 g. yield: 98.3%. mp 129.83-132.70 °C. Integral: -648.91 mJ.
IR (cm-1): 3029.67, 2971.82, 2939.08, 2915.88, 2854.18, 1654.53, 1953.9, 1566.3, 1517.82,
1378.88, 994.8, 813.67, and 736.
1HNMR (CDCl3, 600MHz, ppm) δ: 2.38 (s, 3H), 2.42 (s, 3H), 7.21 (d, 2H, Ј = 8.0), 7.29 (d, 2H, Ј
= 8.1), 7.48 (d, 1H, Ј = 15.6), 7.53 (d, 2H, Ј = 8.0), 7.78 (d, 1H, Ј = 15.6), 7.92 (d, 2H, Ј = 8.1).
13CNMR (CDCl3, 150.92 MHz, ppm) δ: 21.47, 21.61, 121.14, 128.40, 128.59, 129.26, 129.65,
132.28, 135.79, 140.87, 143.42, 144.42, 190.06.
1, 3, 5-Tri-p-tolyl-pentane-1, 5-dione 11. 4-methylacetophenone 9 (2.0 g, 15 mmol) and 1,
3-di-p-tolyl-propenone 10 (3.5 g, 15 mmol) and power NaOH (2.4 g, 60 mmol) were crashed
together with a pestle and mortar for 2 h. Recrystallized from ethanol to give white needle crystal.
Yield: 5.0 g, 90%; Mp.101-104°C.
IR (cm-1): 3060.5, 3031.6, 2975.7, 2941.0, 2914.0, 2892.8, 1677.2, 1669.4, 1606.0, 977.8, 805.4,
and 779.1.
Anal. Cal. For C26H26O: C, 84.29; H, 7.07. Found: C, 84.14; H, 6.98%.
S 7

1HNMR (CDCl3, 400MHz, ppm) δ: 2.27 (s, 3H), 2.39 (s, 6H), 3.34 (m, 4H), 4.00 (m, 1H), 7.06 (d,
2H, Ј = 7.6), 7.15 (d, 2H, Ј = 7.6), 7.22 (d, 4H, Ј = 7.8), 7.84 (d, 4H, Ј = 7.8).
13CNMR (100.61 MHz, CDCl3) δ: 20.52, 21.13, 36.56, 44.51, 126.81, 128.75, 128.78, 134.06,
135.60, 140.45, 143.27, 197.85.
2, 4, 6-tri-p-tolyl-pyridine 12. 4-methylacetophenone (2.0 g, 15 mmol) and 1,
3-Di-p-tolyl-propenone 10 (3.5 g, 15 mmol) and power NaOH (2.4 g, 60 mmol) were crashed
together with a pestle and mortar for 2 h. The yellow powder was added to a stirred solution of
ammonium acetate (10 g, excess) in ethanol (100 mL). The reaction mixture was heated at reflux
for 10 h. Upon cooling to room temperature; a precipitate was filtered, washed with water three
times and dried to afford the product. It was purified by flash column chromatography on silica.
Elution with petroleum/ethyl acetate (10:1) gave a white solid. Yield: 3.2 g, 62.9%. Or 1, 3,
5-Tri-p-tolyl-pentane-1, 5-dione 11 (3.7 g, 10 mmol) added to a stirred solution of ammonium
acetate (8 g, excess) in ethanol (100 mL). The reaction mixture was heated at reflux for 10 h.
Upon cooling to room temperature, a precipitate was filtered, washed with water three times and
dried to afford the product, purified by flash column chromatography on silica. Elution with
petroleum/ethyl acetate (10:1) gave a white solid. Yield: 2.8 g, 75%. Mp: 181-183°C. Integral:
-158.92 mJ.
IR (cm-1): 3027.7, 2962.2, 2919.8, 2858.0, 1600.8, 1543.4, 1510.7, 1422.7, 1389.7, 1184.1,
1114.7, 1018.3, and 809.6.
EI-MS: cal.: 349.18, found: 350.3 (M+).
Anal. Cal. For C26H23N: C, 89.36; H, 6.63; N, 4.01. Found: C, 89.34; H, 6.59; N, 3.97%.
1HNMR (CDCl3, 600MHz, ppm) δ: 2.42 (s, 9H), 7.30 (d, 6H), 7.63 (d, 2H, Ј = 7.8), 7.81 (s, 2H),
8.09 (d, 2H, Ј = 7.9).
13CNMR (CDCl3, 150.92 MHz, ppm) δ: 21.22, 21.29, 116.28, 127.00, 129.36, 129.76, 136.31,
137.00, 138.86, 138.91, 149.87, 157.35.
2, 4, 6-Tris-(4-dimethylphosphorylmethyl-phenyl)-pyridine 13. 2,4,6-Tri-p-tolyl -pyridine 12
(3.5 g, 10 mmol), NBS (5.5 g, 31mmol) and a catalytic amount of benzoyl peroxide (BPO) were
mixed in tetrachloromethane (150 mL). The mixture was refluxed for 5 h. The reaction was
monitored by TLC (petroleum/ethyl acetate 10:1). After the reaction was completed, cooled to
room temperature, it was extracted with chloroform several times. The organic layer was washed
with water and saturated brine consequently. The organic extracts were dried over MgSO4. After
removing solvents under reduced pressure, the residue was collected and dried by vacuum. This
intermediate was added to trimethyl phosphate (50 mL), and the resulting solution was refluxed
for 12hr. The solvent was removed by in vacuo, the residue was purified by flash chromatography
on silica gel using ethyl acetate /ethanol (4:1) as elutent, and gave 2, 4,
6-tris-(4-dimethylphosphoryl methyl-phenyl)-pyridine 13, 4.8 g, 71.3%.
IR (cm-1): 3027.7, 2952.5, 2917.8, 2850.3, 1601.0, 1543.8, 1392.4, 1244.6, 1056.8, 1038.7,
S 8

867.4, 821.0, and 771.4.
EI-Ms: cal.: 673.18, found: (M+) 674.4.
Anal. Cal. For C32H38NO9P3: C, 57.06; H, 5.69; N, 2.08. Found: C, 56.84; H, 5.73; N, 1.97 %.
1HNMR (CDCl3, 600MHz, ppm) δ: 3.27 (d, 6H, Ј = 21.8), 3.72 (dd, 12H), 3.74 (dd, 6H), 7.47 (t,
6H), 7.72 (d, 2H, Ј = 7.9), 7.87 (s, 2H), 8.17 (d, 4H, Ј = 7.9).
13CNMR (CDCl3, 150.92 MHz, ppm) δ: 157.23, 150.03, 138.34, 137.79, 132.74, 132.60 (d, Ј =
9.2 Hz), 130.68 (d, Ј = 6.46 Hz), 130.30 (d Ј = 6.46 Hz), 127.6, 117.1, 53.2 (d, Ј = 6. 64 Hz),
33.01 (d, Ј = 138.29 Hz), 32.89 (d, Ј = 138.45 Hz).
2,6-dip-tolyl-4-(2,6-dip-tolylpyin-4-yl)phenyl)pyridine 15. 4-methylaceto phenone 9 (6.7 g,
50 mmol) and terephthalaldehyde 14 (1.34 g, 10 mmol) and power NaOH (2.4 g, 60 mmol) were
crashed together with a pestle and mortar for 2 h. The yellow powder was added to a stirred
solution of ammonium acetate (15 g, excess) in ethanol (300 mL). The reaction mixture was
heated at reflux for 10 h. Upon cooling to room temperature, a precipitate was filtered, washed
with water three times and dried to afford the product. It was purified by flash column
chromatography on silica. Elution with petroleum/ethyl acetate (2:1) gave a white solid. Yield: 4.8
g, 81.1%.
IR (cm-1): 3027.7, 2952.5, 2917.8, 2850.3, 1601.0, 1543.8, 1392.4, 1244.6, 1056.8, 1038.7,
867.4, 821.0, and 771.4.
EI-Ms: cal.: 592.3, found: 593.5 (M+).
Anal. Cal. For C44H36N2: C, 89.15; H, 6.12; N, 4.73. Found: C, 89.05; H, 6.20; N, 4.61 %.
1HNMR (CDCl3, 400MHz, ppm) δ: 2.44 (s, 12 H), 8.12 (d, 8 H, Ј = 8.0), 7.89 (s, 8 H), 7.33 (d, 8
H, Ј = 8.0).
13CNMR (100.61 MHz, CDCl3) δ: 20.85, 115.88, 126.55, 127.39, 128.97, 136.35, 138.61, 139.30,
148.73, 157.12.
Compound 16. The product was synthesized as described as that of compound 13 using
2,6-dip-tolyl-4-(2,6-dip-tolylpyin-4-yl)phenyl)pyridine 15 (5.9 g, 10 mmol), NBS (8.1 g, 45
mmol) and a catalytic amount of benzoyl peroxide (BPO) were mixed in tetrachloromethane (150
mL). The mixture was refluxed for 5 h. The reaction was monitored by TLC (petroleum/ethyl
acetate 8:1). After the reaction was completed, cooled to room temperature, it was extracted with
chloroform several times. The organic layer was washed with water and saturated brine
consequently. The organic extracts were dried over MgSO4. After removing solvents under
reduced pressure, the residue was collected and dried by vacuum. This intermediate was added to
trimethyl phosphate (150 mL), and the resulting solution was refluxed for 12hr. The solvent was
removed by in vacuo, the residue was purified by flash chromatography on silica gel using ethyl
acetate/ethanol (4:1) as elutent, and gave compound 16. Yield: 4.3 g, 41.3%.
MALDI-TOF, m/z: cal.: 1024.36, found: 1025.5.
1HNMR (CDCl3, 400MHz, ppm) δ: 3.27 (d, 8 H, Ј = 21.9), 3.72 (d, 24 H, Ј = 10.8), 7.47 (dd, 8 H,
Ј = 8.0, 2.4), 7.9 1 (s, 4 H), 7.93 (s, 4 H), 8.18 (d, 8 H, Ј = 8.0).
S 9

13CNMR (CDCl3, 100.62 MHz, ppm) δ: 32.3 (d, Ј = 138.2), 52.5 (d, Ј = 6.8), 116.45, 126.97(d,
Ј = 3.2), 127.45, 129.68 (d, Ј = 6.6), 132.03 (d, Ј = 9.4), 137.57, 139.14, 149.01, 156.75.
Compound G0
Fresh t-BuOK (202 mg, 1.8 mmol) was placed a dry mortar and milled to very small, then
compound 13 (135 mg, 0.2 mmol) and 5 (508 mg, 0.66 mmol) were added and mixed equably.
The mixture was milled vigorously for about 15 min. The mixture became sticky and 1 g
anhydrous Na2SO4 was added, then continuously milled for 10 min. After completion of the
reaction (the reaction was monitored by TLC (petroleum/ CH2Cl2 5:1), the mixture was dispersed
in 100 mL water. The solution was extracted with CH2Cl2 three times. The organic layer was
washed with water and saturated brine consequently. The organic extracts were dried over MgSO4.
The solvent was removed by in vacuo, the residue was transferred to the top of a silica gel
chromatography column which was eluted with petroleum ether / CH2Cl2 (8: 1). The strong green
fluorescence was collected and 302 mg product G0 was obtained with 58.1% yield.
MALDI-TOF, m/z: cal.: 2603.36, found: 2602.7 (M+). Shown in Figure. S2.
Anal. Cal. For C191H170N10: C, 88.05; H, 6.58; N, 5.38. Found: C, 87.91; H, 6.67; N, 5.29 %.
1HNMR (CDCl3, 400MHz, ppm) δ: 0.96 (m, 27 H), 1.42 (m, 18 H), 1.89 (m, 18 H), 4.33 (m, 18
H), 7.20-7.26 (m, 6 H), 7.40-7.70 (m, 23 H), 7.73-7.82 (m, 18 H), 8.04-8.13 (m, 19 H), 8.22 (s, 2
H), 8.37 (m, 9 H), 8.68 (s, 3 H), 8.75 (s, 6 H), 8.80 (s, 3 H).
13CNMR (CDCl3, 100.62 MHz, ppm) δ: 13.54, 20.13, 29.23, 42.51, 108.39, 108.51, 118.47,
118.68, 120.06, 122.59, 122.96, 123.05, 124.22, 124.98, 125.17, 125.31, 132.16, 139.64, 140.02,
140.50, 142.79.
Compound G1. The product G1 was synthesized as described above compound G0 using
compound 16 and 5 in the present of fresh t-BuOK under solventless conditions. Yield: 40%.
1H-NMR δ (ppm): 0.95 (m, 36 H), 1.41 (m, 24 H), 1.88 (m, 24 H), 4.33 (t, 24 H, Ј =7.04),
7.19-7.26 (overlapping multiplets, 18 H), 7.34-7.51 (overlapping multiplets, 36 H), 7.67 (t, 12 H),
7.84 (d, 8 H), 7.90 (dd, 12 H), 8.03 (s, 12 H), 8.19 (d, 16 H), 8.33 (s, 4 H), 8.51 (s, 12 H).
13CNMR δ 13.42, 20.11, 30.72, 40.48, 108.36, 108.48, 108.60, 118.44, 118.67, 120.05, 122.56,
122.95, 123.00, 123.04, 124.20, 124.36, 124.96, 125.15, 125.30, 126.96, 127.33, 128.17, 129.81,
132.15, 132.38, 139.62, 140.01, 140.40, 140.48, 142.53, 142.79.
MALDI-TOF, m/z: cal.: 3597.86, found: 3597.8 (M+). Shown in Figure. S3.
S 10

A computer generated 3D model of G1 (space filling)
S 11

A computer generated 3D model of G1 (ball and stick)
S 12

A computer generated 3D model of G0 (space filling)
S 13

A computer generated 3D model of G0 (ball and stick)
S 14

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Figure S-1
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Figure S-2
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Figure S-3
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