A cationic water-soluble pillar[5]arene: synthesis and ... · S1 A cationic water-soluble...

S1

A cationic water-soluble pillar[5]arene: synthesis and host − guest complexation with sodium 1-octanesulfonate

Yingjie Ma,a Xiaofan Ji,a Fei Xiang,a Xiaodong Chi,a Chengyou Han,a Jiuming He,b Zeper Abliz,b Weixiang Chena and Feihe Huanga,*

a Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China, and Fax: +86-571- 8795-1895;

Tel: +86-571-8795-3189; Email address: [email protected].

b Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing

100050, P. R. China.

Electronic Supplementary Information (13 pages)

1. Materials and methods S2

2. Syntheses of compounds 1, 2 and 3 S3

3. Stoichiometry and association constant determination for the complexation between

1 and G

S10

4. Electrospray ionization mass spectrum of an equimolar water solution of 1 and G S12

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011

S2

1. Materials and methods

All reagents were commercially available and used as supplied without further purification. NMR spectra were

recorded with a Bruker Advance DMX 500 spectrophotometer or a Bruker Advance DMX 400 spectrophotometer

with use of the deuterated solvent as the lock and the residual solvent or TMS as the internal reference.

Low-resolution electrospray ionization mass spectra were recorded with a Bruker Esquire 3000 Plus 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). The melting points were collected on a SHPSIC WRS-2 automatic melting point apparatus.


S3

2. Synthesis of 1

Scheme S1. Synthesis of 1.

2.1. Synthesis of compound 2 S1

Carbon tetrabromide (39.8 g, 120 mmol) was slowly added in small portions to a solution of

1,4-bis(2-hydroxyethoxy)benzene (10.0 g, 50.4 mmol) and triphenylphosphine (31.5 g, 120 mmol) in 300 mL of

dry acetonitrile at 0 °C with stirring. The reaction mixture was allowed to warm to room temperature, and the

resulting clear solution was stirred for another 4 h under N2. Then 200 mL of cold water was added to the reaction

mixture, where product 2 precipitated as a white solid. The product was collected by vacuum filtration, thoroughly

washed with methanol/water 60:40, and then recrystalized from methanol. The white flake-like crystals were dried

under high vacuum (13.8 g, 85 %). The 1H NMR spectrum of 2 is shown in Figure S1. 1H NMR (400 MHz,

chloroform-d, room temperature) δ (ppm): 6.89 (s, 4H), 4.27 (t, J = 6.3 Hz, 4H), 3.64 (t, J = 6.3 Hz, 4H).


S4

3.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.0f1 (ppm)

Fig. S1. 1H NMR spectrum (400 MHz, chloroform-d, room temperature) of 2.

2.2. Synthesis of compound 3S2

To a solution of 2 (3.37 g, 11.5 mmol) in 1, 2-dichloroethane (200 mL), paraformaldehyde (0.349 g, 11.5 mmol)

was added under nitrogen atmosphere. Then boron trifluoride diethyl etherate (BF3·(OC2H5)2, 1.63 g, 11.5 mmol)

was added to the solution and the mixture was stirred at room temperature for 3 h. A green solution was got. After

the solvent was removed, the obtained solid was purified by column chromatography on silica gel with petroleum

ether/dichloromethane (1:2 v/v) as the eluent to get a white powder (1.6 g, 41 %). Mp: 95.0−97.0 °C. The 1H NMR

spectrum of 3 is shown in Figure S2. 1H NMR (400 MHz, chloroform-d, room temperature) δ (ppm): 6.93 (s, 10H),


S5

4.25 (t, J = 5.7 Hz, 20H), 3.86 (s, 10H), 3.65 (t, J = 5.7 Hz, 20H). The 13C NMR spectrum of 3 is shown in Figure

S3. 13C NMR (125 MHz, chloroform-d, room temperature) δ (ppm): 149.58, 128.97, 116.00, 68.88, 30.65, and

29.32. LRESIMS is shown in Figure S4: m/z 1702.5 [M + Na]1+ (100%). HRESIMS is shown in Figure S5: m/z

calcd for [M + Na]+ C55H60Br10O10, 1702.5938; found 1702.58.

3.73.94.14.34.54.74.95.15.35.55.75.96.16.36.56.76.97.1f1 (ppm)

Fig. S2. 1H NMR spectrum (400 MHz, chloroform-d, room temperature) of 3.

3035404550556065707580859095100105110115120125130135140145150f1 (ppm)

Fig. S3. 13C NMR spectrum (125 MHz, chloroform-d, room temperature) of 3.

CDCl3


S6

947.3 1092.9 1200.91384.9

1702.5

+MS, 0.0-0.1min (#1-#8)

0

1

2

3

5x10Intens.

900 1000 1100 1200 1300 1400 1500 1600 1700 1800 m/z

Fig. S4. Electrospray ionization mass spectrum of 3.

C55H60Br10O10

1700 1750m/z

0

50

100Relative Intensity

1702.58

Fig. S5. High resolution electrospray ionization mass spectrum of 3.

[M + Na]+

[M + Na]+


S7

2.2. Synthesis of compound 1

NMe3

C2H5OH

13

H

H

O

O5

Br

Br

H

H

O

O5

N

N 10Br95 %

Compound 3 (1.00 g, 0.595 mmol) and trimethylamine (33 % in ethanol, 6.43 mL, 23.8 mmol) were added to

ethanol (50 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 (1.28 g, 95 %). Mp: 101.0−103.0 °C. The 1H NMR spectrum of 1 is shown in Figure

S6. 1H NMR (400 MHz, D2O, room temperature) δ (ppm): 6.98 (s, 10H), 4.48 (s, 20H), 3.94 (s, 10H), 3.84 (s, 20H),

3.24 (s, 90H). The 13C NMR spectrum of 1 is shown in Figure S7. 13C NMR (125 MHz, D2O, room temperature) δ

(ppm): 149.30, 129.89, 116.55, 64.91, 63.49, 54.13, and 29.57. LRESIMS is shown in Figure S8: m/z 1055.12 [M −

2Br]2+, 677.11 [M − 3Br]3+, 487.66 [M − 4Br]4+, 374.31 [M − 5Br]5+, 298.46 [M − 6Br]6+. HRESIMS is shown in

Figure S9: m/z of C85H150Br10N10O10 1055.25 [M − 2Br]2+, 677.19 [M − 3Br]3+, 487.66 [M − 4Br]4+, 374.35 [M −

5Br]5+, 298.47 [M − 6Br]6+.

3.03.54.04.55.05.56.06.57.0f1 (ppm)

Figure S6. 1H NMR spectrum (400 MHz, D2O, room temperature) of 1.

D2O


S8

253035404550556065707580859095100105110115120125130135140145150155f1 (ppm)

Figure S7. 13C NMR spectrum (125 MHz, D2O, room temperature) of 1.

Ionization Mode: 1:ESI+ Instrument Conf iguration: JMS-T100LC Acq. Data Name: H Time of Maximum: 0.000[min]

500 1000 1500 2000m/z

0

500

1000

Intensity (1179)

298.46298.79374.31

298.96 373.91298.12 677.11

374.71286.57 676.45677.44279.40

678.11 1055.12678.78

1057.621021.20 1434.53 1966.931631.69

Figure S8. Electrospray ionization mass spectrum of 1.


S9

C85H150Br8N10O10

1030 1040 1050 1060 1070m/z

0

50


1055.25

C85H150Br7N10O10

675 680 685 690m/z

0

50


677.19

C85H150Br6N10O10

482 484 486 488 490 492m/z

0

50


487.66

[M − 2Br]2+

[M − 3Br]3+

[M − 4Br]4+


S10

C85H150Br5N10O10

372.0 374.0 376.0 378.0 380.0m/z

0

50


374.35

C85H150Br4N10O10

298.0 300.0 302.0m/z

0

50


298.47

Figure S9. High resolution electrospray ionization mass spectra of 1.

3. Stoichiometry and association constant determination for the complexation between 1 and G

To determine the stoichiometry and association constant between 1 and octyl sodium sulfonate (G), 1H NMR titrations were done with solutions which had a constant concentration of G (16 mM) and

varying concentrations of 1. By a non-linear curve-fitting method, the association constant between the

guest and 1 was calculated. By a mole ratio plot, a 1:1 stoichiometry was obtained; the guest was shown

to form a 1:1 complex with 1.

The non-linear curve-fitting was based on the equation:S3 Δδ = (Δδ∞/[G]0) (0.5[H]0 + 0.5([G]0+1/Ka)−(0.5 ([H]0

2+(2[H]0(1/Ka − [G]0)) + (1/Ka + [G]0)2) 0.5)) (Eq. S1)

Where Δδ is the chemical shift change of H1 on G at [H]0, Δδ∞ is the chemical shift change of H1 when the

guest is completely complexed, [G]0 is the fixed initial concentration of the guest, and [H]0 is the varying

concentrations of 1.

[M − 5Br]5+

[M − 6Br]6+


S11

Figure S10. 1H NMR spectra (D2O, 293 K, 400 MHz) of G at a concentration of 16 mM upon different concen-

trations of 1: (a) 0.00 mM, (b) 3.07 mM, (c) 5.92 mM, (d) 8.57mM, (e) 11.03 mM, (f) 13.89 mM, (g) 16.51 mM, (h)

21.18 mM, (i) 25.21 mM, (j) 31.81 mM, (k) 36.99 mM, (l) 44.60 mM, (m) 49.92 mM.

-0.005 0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035 0.040 0.045 0.050 0.055-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Che

mic

al s

hift

chan

ges

of H

1 on

G (p

pm)

[H]0

Figure S11. The chemical shift changes of H1 on G upon addition of 1. The red solid line was obtained from the

non-linear curve-fitting using Eq. S1.

R2 = 0.998 Ka = (1.33 ± 0.936) × 104 M-1


S12

0.0 0.2 0.4 0.6 0.8 1.00.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

[H] 0/[G

] 0

Chemical shift changes of H1 on G (ppm)

Figure S12. Mole ratio plot for the complexation between 1 and G, indicating a 1:1 stoichiometry. 4. Electrospray ionization mass spectrum of an equimolar water solution of 1 with G.

R2 = 0.998

R2 = 0.853


S13

Ionization Mode: 1:ESI+ Instrument Conf iguration: JMS-T100LC Acq. Data Name: H+G4 Time of Maximum: 0.000[min]

260 270 280 290 300 310 320m/z

0

200

400

600

800Intensity (819)

276.37

276.20 317.52276.53

276.03 298.23317.18276.70

298.43 314.20276.87260.75 272.71

311.53280.22270.39 302.03291.51268.35

Figure S13. Electrospray ionization mass spectrum of an equimolar water solution of 1 with G. Assignment of

main peaks: m/z 276.37 [1⊃G − 7Br]7+, 298.23 [1 − 6Br]6+.

References：

S1. M.R. Pinto, B.M. Kristal and K.S. Schanze, Langmuir, 2003, 19, 6523−6533.

S2. T. Ogoshi, S. Kanai, S. Fujinami, T. A. Yamagishi and Y. Nakamoto, J. Am. Chem. Soc., 2008, 130, 5022−5023.

S3. P. R. Ashton, R. Ballardini, V. Balzani, M. Belohradsky, M. T. Gandolfi, D. Philp, L. Prodi, F. M. Raymo, M.

V. Reddington, N. Spencer, J. F. Stoddart, M.Venturi and D. J. Williams, J. Am. Chem. Soc., 1996, 118,

4931−4951.

[1�G – 7Br]7+

[1 – 6Br]6+


A cationic water-soluble pillar[5]arene: synthesis and ... · S1 A cationic water-soluble...

Documents

Transcript of A cationic water-soluble pillar[5]arene: synthesis and ... · S1 A cationic water-soluble...