a cationic water-soluble pillar[6]arene: synthesis, host ... · a cationic water-soluble...

S1

A Cationic Water-Soluble Pillar[6]arene: Synthesis,

Host–Guest Properties, and Self-Assembly with Amphiphilic

Guests in Water

Yingjie Ma, Jie Yang, Jinying Li, Xiaodong Chi, and Min Xue *

Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China Fax:

+86-571-8795-3189MOE; E-mail: [email protected]

Supporting Information (13 pages)

1. Materials and methods S2

2. Synthesis of 4S1 S3

3. Synthesis of 2 and 3 S4

4. Synthesis of 1 S8

5. Synthesis of G2 S10

6. Fluorescence titration experiments of 1 and G1 S12

7. References S13

Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013

S2

1. Materials and methods

All commercial reagents were used as received. Solvents were either employed as

purchased or dried according to procedures described in the literature. 1H NMR

spectra were collected on a Varian Unity INOVA-400 spectrometer with internal

standard TMS. 13C NMR spectra were recorded on a Varian Unity INOVA-400

spectrometry at 100 MHz. The melting points were collected on a SHPSIC WRS-2

automatic melting point apparatus. Mass spectra were performed on a Bruker Esquire

3000 plus mass spectrometer (Bruker-Franzen Analytik GmbH Bremen, Germany)

equipped with ESI interface and ion trap analyzer. High resolution mass spectra were

obtained on a Bruker 7-Tesla FT-ICRMS equipped with an electrospray source

(Billerica, MA, USA). MALDI-TOF-MS spectra were performed on a AXIMA

Performance-MALDI TOF/TOF (Matrix: 2,5-dihydroxy-benzoic acid).


S3

2. Synthesis of 4S1

A mixture of dibromobutane (77.7 g, 360 mmol), hydroquinone (9.90 g, 90 mmol),

and potassium carbonate (37.26 g, 0.27 mol) in 60 mL acetone was refluxed under N2

for 24 h. The reaction mixture was concentrated in vacuo and the resulting residue

was partitioned between 150 mL water and 150 mL chloroform. The organic layer

was evaporated to dryness and the precipitate was washed with sodium hydroxide

solution (3×50 mL, 1 N ), water (2×50 mL), and n-hexane (2×50 mL), and dried in

vacuo to give 4 as a white solid 18.8 g (55 %). 1H NMR (400 MHz, chloroform-d,

room temperature) δ (ppm): 6.81 (s, 4H), 3.94 (t, J = 6 Hz, 4H), 3.48 (t, J = 6 Hz, 4H),

2.03–2.10 (m, 4H), 1.88–1.95 (m, 4H).

Figure S1. 1H NMR spectrum (100 MHz, chloroform-d, room temperature) of 4.


S4

3. Synthesis of 2 and 3

To a solution of 4 (1.95 g, 5.00 mmol) in 1, 2-dichloroethane (50 mL),

paraformaldehyde (0.181 g, 6.00 mmol) was added at 20 °C. Then, boron trifluoride

diethyl etherate (BF3•(OC2H5)2, 0.71 g, 5.00 mmol) was added to the solution and the

mixture was stirred at 20 °C for 10 min. Then saturated NaHCO3 aqueous solution (50

mL) was added. The organic layer was dried over anhydrous Na2SO4 and evaporated

to afford the crude product, which was isolated by flash column chromatography

using petroleum ether/dichloromethane (v/v = 2:1) as the eluent to give the product, 2

and 3. 2 was a colorless oil (0.110 g, 6%). 3 was a white solid (0.52 g, 27 %, Mp:

91.293.1 C). 3 was separated firstly, and then was 2 eluted out. 2: 1H NMR (400

MHz, chloroform-d, room temperature) δ (ppm): 6.67 (s, 12H), 3.79–3.83 (m, 36H),

3.40 (t, J = 6.4 Hz, 24H), 1.93–1.99 (m, 24H), 1.82–1.87 (m, 24H). 13C NMR (100

MHz, chloroform-d, room temperature) (ppm): 150.39, 127.94, 114.90, 67.70, 33.85,

29.73, 29.61, 28.33. MALDI-TOF-MS: m/z calcd for [M]+ C90H120Br12O12, 2351.8858

(100.0%), 2353.8837 (83.4%), found 2353.2. 3: 1H NMR (400 MHz, chloroform-d,

room temperature) δ (ppm): 6.84 (s, 10H), 3.95 (s, 20H), 3.76 (s, 10H), 3.47 (t, J = 6.1

Hz, 20H), 2.08 (s, 20H), 1.96 (m, 20H). 13C NMR (100 MHz, chloroform-d, room

temperature) (ppm): 150.39, 127.94, 114.90, 67.70, 33.85, 29.73, 29.61, 28.33.

MALDI-TOF-MS: m/z calcd for [M]+ C75H100Br10O10, 1959.9048 (100.0%),

1960.9081 (81.1%), found 1960.7.


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Figure S3. 13C NMR spectrum (100 MHz, chloroform-d, room temperature) of 2.


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2300 2320 2340 2360 2380 2400 2420 2440 24600

10000

20000

30000

40000

50000

% in

t

m/z

2353.2

Figure S4. MALDI-TOF-MS of 2.



S7

Figure S6. 13C NMR spectrum (100 MHz, chloroform-d, room temperature) of 3.

1940 1950 1960 19700

50000

100000

150000

200000

% in

t

m/z

1960.7

Figure S7. MALDI-TOF-MS of 3.


S8

4. Synthesis of 1

NMe3

C2H5OH

12

H

H

O

O6

H

H

O

O6

12Br

Br

Br

N

N

97 %

Compound 2 (1.30 g, 0.556 mmol) and trimethylamine (33 % in ethanol, 9 mL, 3.33

mmol) were added to ethanol 20 mL. The solution was refluxed overnight. Then the

solvent was removed by evaporation, deionized water 20 mL was added. After

filtration, a clear solution was got. Then the water was removed by evaporation to

obtain 1 as a colorless solid (1.65 g, 97 %). Mp 210-212 °C. 1H NMR (400 MHz, D2O,

room temperature) δ (ppm): 6.83 (s, 12H), 3.91 (t, J = 4.0 Hz, 24H), 3.82 (s, 12H),

3.19 (t, J = 4.0 Hz, 24H), 2.95 (s, 108H), 1.71 (m, 48H). The 13C NMR spectrum of 4

is shown in Figure S7. 13C NMR (125 MHz, D2O, room temperature) δ (ppm): 150.25,

129.31, 116.85, 68.76, 66.13, 52.94, 30.14, 25.87, 19.55. LRESIMS is shown in

Figure S10: m/z 532.45 [M 5Br]5+. HRESIMS is shown in Figure S11: m/z of

C126H228Br12N12O12 532.45 [M 5Br]5+.


S9

Figure S8. 1H NMR spectrum (400 MHz, D2O, room temperature) of 1

Figure S9. 13C NMR spectrum (125 MHz, D2O, room temperature) of 1.


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Ionization Mode: 1:ColdSpray+ Instrument Conf iguration: JMS-T100LC Acq. Data Name: H2

Experiment Date/Time: 11/9/2012 9:45:36 AM Time of Maximum: 0.082[min]

500 520 540 560m/z

0

5

10

15

20

25

30

35

Intensity (36307)x103

532.45

494.43

501.81504.22

513.65

520.63527.50

536.18555.66 558.28

Figure S10. Electrospray ionization mass spectrum of 1.

Ionization Mode: 1:ColdSpray+ Instrument Conf iguration: JMS-T100LC Acq. Data Name: H2

Experiment Date/Time: 11/9/2012 9:45:36 AM Time of Maximum: 0.082[min]

530.0 532.0 534.0m/z

5

10

15

20

25

30

Intensity (32852)x103

532.45

531.22

531.44

531.66

531.82

532.04

532.23

532.83

532.64

533.04

533.24

533.62

Figure S11. High resolution electrospray ionization mass spectroscopy of 1.

5. Synthesis of G2

To a solution of sodium 6-hydroxynaphthalene-2-sulfonate (2.95 g, 12.0 mmol) in

water (50 mL), 1-bromodadecane (5.98 g, 24.0 mmol), NaOH (0.96 g, 24 mmol) and

ethanol (50 mL) were added. The mixture was refluxed overnight and then filtrated to

get a yellow solid. After washed with dichloromethane and ethanol, a white solid was


S11

obtained (2.6 g, 52 %). 1H NMR (400 MHz, DMSO-d6, room temperature) δ (ppm):

8.04 (s, 1H), 7.86 (d, J = 8.9 Hz, 1H), 7.72 (d, J = 8.5 Hz, 1H), 7.64 (d, J = 8.3 Hz,

1H), 7.29 (s, 1H), 7.15 (d, J = 8.8 Hz, 1H), 4.08 (t, J = 6.4 Hz, 2H), 1.77 (t, J = 6.4 Hz,

2H), 1.45 (m, 2H), 1.25 (m, 16H), 0.84 (t, J = 6.4 Hz, 3H).

Figure S12. 1H NMR spectrum (400 MHz, DMSO-d6, room temperature) of G2.


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6. Determination of association constant for the complex between 1 and G1 by

fluorescence titration experiments.

300 350 400 450

0

100

200

300

400

500

600

700

800C

1/C

G1

0.00 0.10 0.20 0.29 0.38 0.50 0.61 0.83 1.03 1.42 1.77

Flu

ore

scen

ce In

ten

sity

(a

.u.)

Wavelength (nm)

-11.5 -11.0 -10.5 -10.0 -9.5 -9.0 -8.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

ln[(

F0-

F)/

F]

ln(1)

Figure S13. Fluorescence emission spectra of G1 (1.00 × 10–4 M, λex = 274 nm) in

water at 298 K with different concentrations of 1 (from 0 to 1.77 × 10–4 M) (top) and

the plot of the Stern-Volmer equation ln (F0/ F – 1) = lnK + nln [1]S2 for the

complexation using the fluorimetric titration data at λem = 339 nm. F0 is the initial

fluorescent emission intensity of G1 and F is the fluorescent emission intensity of G1

in the presence of different concentrations of 1 (bottom).

R2 = 0.997

Ka = (2.45±0.20) × 104 M-1

H/G1 =1


S13

References:

S1. P. Wei, X. Yan, J. Li, Y. Ma and F. Huang, Chem. Commun., 2013, 49,

1070–1072.

S2. G. Yu, Z. Zhang, C. Han, M. Xue, Q. Zhou and F. Huang, Chem. Commun., 2012,

48, 2958–2960.


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