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Electronic Supplementary Information

Pillar[n]arenes (n = 8-10) with Two Cavities: Synthesis,

Structures and Complexing Properties

Xiao-Bo Hu,1 Zhenxia Chen,1 Lei Chen,1 Ling Zhang,2 Jun-Li Hou,*,1 and Zhan-Ting Li1

1
Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433, China
2
Honeywell Integrated Technology (China) Co. Ltd., 430 Li Bing Road, Shanghai, 201203, China

*To whom correspondence should be addressed: houjl@fudan.edu.cn

Contents:
1. General S2
2. Synthetic procedure for PA[n] (n = 5-10) S2
3. Characterization data and spectra for PA[n] (n = 5-10) S2
4. Comparing the 1H NMR and 13
C NMR spectra of PA[n] (n = 5-10) S8
5. Variable temperature 1H NMR experiments S9
6. 1H NMR titration experiments S9
7. HR ESI-MS experiments S13
8. 2D 1H NMR NOESY experiment S14
9. References S14

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1. General:
1 13
H and C NMR spectra were recorded at 400 MHz with a Mercury plus 400
spectrometer at 298 K. Chemical shifts were referenced to CHCl3 residue (7.26 ppm
for 1H NMR, 77.0 ppm for 13
C NMR). Mass spectra were recorded with Bruker
MicroTOF II spectrometer. 1,4-diethoxybenzene and paraformaldehyde were obtained
from Alfa Aesar. For single crystal growing, PA[8], PA[9] and PA[10] (2-5 mg) were
respectively dissolved in acetonitrile, DMF, and acetone (0.3 ml). The single crystals
were obtained by slow evaporation the solutions under 20 oC for 2-4 weeks. For the
all three crystals, the data sets were treated with the SQUEEZE program to remove
highly disordered solvent molecules. The crystallographic formulae include the
number of solvent molecules suggested by the SQUEEZE program.

2. Synthetic procedure for PA[n] (n = 5-10):

To the solution of 1,4-diethoxybenzene (6.00 g, 36 mmol) in chloroform (300 ml)
was added paraformaldehyde (1.08 g, 36 mmol). The suspension was stirred at 25 oC
for 20 min to crush the large paraformaldehyde particles. And then, boron trifluoride
diethyl etherate (4.5 ml, 36 mmol) was added to the solution. After continuing stirred
at 25 oC for 20 min, the reaction was quenched by addition of water. The organic
phase was separated and washed with saturated aqueous NaHCO3, H2O, and brine.
The crude product was purified by column chromatograph (CH2Cl2/petroleum ether)
to yield PA[5] (CH2Cl2/petroleum ether = 1 : 1, Rf = 0.2, 1.28 g, 20%), PA[6]
(CH2Cl2/petroleum ether = 4 : 1, Rf = 0.3, 0.96 g, 15%), PA[7] (CH2Cl2/petroleum
ether = 10 : 1, Rf = 0.3, 192 mg, 3%), PA[8] (CH2Cl2/petroleum ether = 30 : 1, Rf =
0.3, 64 mg, 1%), PA[9] (CH2Cl2/petroleum ether = 50 : 1, Rf = 0.2, 126 mg, 2%), and
PA[10] (CH2Cl2/petroleum ether = 100 : 0, Rf = 0.2, 130 mg, 2%) as white solids.

3. Characterization data and spectra for PA[n] (n = 5-10):

PA[5][1]: 1H NMR (CDCl3, 400 MHz): δ 6.72 (s, 10 H), 3.83 (q, J = 6.4 Hz, 20 H),
13
3.76 (s, 10 H), 1.26 (t, J = 6.4 Hz, 30 H). C NMR (CDCl3, 100 MHz): δ 149.8,
128.4, 115.0, 63.7, 29.8, 15.1.

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6.72

3.84
3.82
3.76

1.28
1.26
1.25
ppm (t1) 5.0 0.0

Figure S1. 1H NMR spectrum of PA[5] in CDCl3.

149.8

128.4

115.0

63.7

29.8

15.1
ppm (t1) 150 100 50 0

Figure S2. 13C NMR spectrum of PA[5] in CDCl3.

PA[6][1]: 1H NMR (CDCl3, 400 MHz): δ 6.69 (s, 12 H), 3.83 (q, J = 6.4 Hz, 24 H),
3.79 (s, 12 H), 1.28 (t, J = 6.4 Hz, 36 H). 13C NMR (CDCl3, 100 MHz): δ 150.4,
127.8, 115.2, 64.0, 30.9, 15.2.
6.69

3.84
3.82
3.81
3.79

1.30
1.29
1.27

ppm (t1) 5.0 0.0

Figure S3. 1H NMR spectrum of PA[6] in CDCl3.

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150.4

127.8

115.2

64.0

30.9

15.2
ppm (t1) 150 100 50 0
13
Figure S4. C NMR spectrum of PA[6] in CDCl3.

PA[7]: 1H NMR (CDCl3, 400 MHz): δ 6.63 (s, 14 H), 3.83 (s, 14 H), 3.79 (q, J = 6.4
Hz, 28 H), 1.22 (t, J = 6.4 Hz, 42 H). 13C NMR (CDCl3, 100 MHz): δ 150.6, 127.9,
115.2, 64.2, 31.0, 15.1. MS (ESI): m/z 1269 [M+Na]+, HR-MS (ESI-TOF): Calcd. for
C77H98O14Na: 1269.6854. Found: 1269.6822.
6.63

3.83
3.80
3.78

1.24
1.22
1.21

ppm (t1) 5.0 0.0

Figure S5. 1H NMR spectrum of PA[7] in CDCl3.

150.6

127.9

115.2

64.2

31.0

15.1

ppm (t1) 150 100 50 0

Figure S6. 13C NMR spectrum of PA[7] in CDCl3.

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Figure S7. HR ESI-MS of PA[7].

PA[8]: 1H NMR (CDCl3, 400 MHz): δ 6.61 (s, 16 H), 3.84 (s, 16 H), 3.80 (q, J = 6.8
Hz, 32 H), 1.23 (t, J = 6.8 Hz, 48 H). 13C NMR (CDCl3, 100 MHz): δ 150.6, 127.8,
114.9, 64.2, 30.4, 15.0. MS (ESI): m/z 1448 [M+Na]+, HR-MS (ESI-TOF): Calcd. for
C88H112O16Na: 1447.7848. Found: 1447.7841.
6.61

3.84
3.82
3.81
3.79
3.77

1.24
1.23
1.21

ppm (t1) 5.0 0.0

Figure S8. 1H NMR spectrum of PA[8] in CDCl3.

150.6

127.8

114.9

64.2

30.4

15.0

ppm (t1) 150 100 50 0

Figure S9. 13C NMR spectrum of PA[8] in CDCl3.

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Figure S10. HR ESI-MS of PA[8].

PA[9]: 1H NMR (CDCl3, 400 MHz): δ 6.64 (s, 18 H), 3.83 (s, 18 H), 3.82 (q, J = 6.8
Hz, 36 H), 1.26 (t, J = 6.8 Hz, 54 H). 13C NMR (CDCl3, 100 MHz): δ 150.4, 127.9,
114.9, 64.1, 30.0, 15.1. MS (ESI): m/z 1627 [M+Na]+, HR-MS (ESI-TOF): Calcd. for
C99H126O18Na: 1626.8875. Found: 1626.8860.
6.64

3.85
3.83
3.81
3.79

1.27
1.26
1.24

ppm (t1) 5.0 0.0

Figure S11. 1H NMR spectrum of PA[9] in CDCl3.

150.4

127.9

114.9

64.1

30.0

15.1

ppm (t1) 150 100 50 0

Figure S12. 13C NMR spectrum of PA[9] in CDCl3.

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Figure S13. HR ESI-MS of PA[9].

PA[10]: 1H NMR (CDCl3, 400 MHz): δ 6.65 (s, 20 H), 3.83 (s, 20 H), 3.82 (q, J = 6.6
Hz, 40 H), 1.26 (t, J = 6.6 Hz, 60 H). 13C NMR (CDCl3, 100 MHz): δ 150.5, 127.9,
114.9, 64.2, 30.0, 15.1. MS (ESI): m/z 1805 [M+Na]+, HR-MS (ESI-TOF): Calcd. for
C110H140O20Na: 1804.9869. Found: 1804.9894.
6.65

3.85
3.83
3.82
3.80

1.28
1.26
1.25

ppm (t1) 5.0 0.0

Figure S14. 1H NMR spectrum of PA[10] in CDCl3.

150.5

127.9

114.9

64.2

30.0

15.1

ppm (t1) 150 100 50 0

Figure S15. 13C NMR spectrum of PA[10] in CDCl3.

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Figure S16. HR ESI-MS of PA[10].

4. Comparing the 1H NMR and 13C NMR spectra of PA[n] (n = 5-10):

a) Ar-H Bridge-H b) Ar-C Bridge-C

PA[5]

PA[6]

PA[7]

PA[8]

PA[9]

PA[10]

6.80 6.50 4.00 3.60 152.0 149.0 32.0 28.0

ppm ppm
Figure S17. Partial (a) 1H NMR (400 MHz, 2.0 mM) and (b) 13
C NMR (100 MHz,
10.0 mM) spectra of PA[n]s (n = 5-10) in CDCl3 at 25 oC.

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5. Variable temperature 1H NMR experiments:

a)

b)

ppm (t1) 7.0 6.0 5.0 4.0

Figure S18. 1H NMR spectra of PA[10] at (a) 25 °C and (b) -50 °C, indicating no
signal splitting or broadening.

6. 1H NMR titration experiments:

To determine the association constants (Ka) for PA[n]s (n = 5, 6, 9, 10) binding with
OTA, 1H NMR titration experiments were done with CDCl3 solutions which had a
constant concentration of PA[n] (1.0 mM) and varying concentration of OTA.
From the molar ratio plot, a 1:1 stoichiometry was obtained for PA[5], PA[6] and
PA[9] binding with OTA. The association constants (Ka) of them were estimated by a
non-linear curve-fitting method with the equation:[2]
Δδ = (Δδ∞/[H]){0.5([G] + [H] + 1/Ka) – (([G] + [H] + 1/Ka)2 + 4[H][G])0.5} Eq. 1
Where Δδ is the chemical shift change of ArH on PA[n]s (n = 5, 6, 9) at [G], Δδ∞ is
the chemical shift change of ArH when PA[n]s is completely complexed, [H] is the
fixed initial concentration of the host, and [G] is the concentration of OTA.
From the molar ratio plot, a 1:2 stoichiometry was obtained for PA[10] binding
with OTA. The association constant (Ka) was estimated by a non-linear curve-fitting
method with the equation:[2]
Δδ = (ΔδHGK1[G] + ΔδHG2K1K2[G]2) / (1 + K1[G] + K1K2[G]2) Eq. 2
Where Δδ is the chemical shift change of ArH on PA[10] at [G], ΔδHG is the chemical
shift change of ArH when PA[10] is completely complexed by the first OTA, ΔδHG2 is
the chemical shift change of ArH when PA[10] is completely complexed by the
second OTA, [H] is the fixed initial concentration of the host, and [G] is the

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concentration of OTA.

0.15
0.15

R2 = 0.983
Δδ (ppm)

0.10
0.10
Ka = 2.4 (±0.1) × 10 3 M -1

0.05
0.05

0.00
0
00 0.001 2
0.002 0.003 4
0.004
[OTA] (M)
Figure S19. Changes of the chemical shift changes of ArH on PA[5] with addition of
OTA. The red solid line was obtained from the non-linear curve-fitting with Eq. 1.
0.16
0.16

0.14

0.12
0.12

0.10
R2 = 0.989
Δδ (ppm)

Ka = 1.2 (±0.1) × 10 3 M -1
0.08
0.08

0.06

0.04
0.04

0.02

0.00
0
00 1
0.001 2
0.002 3
0.003 4
0.004
[OTA] (M)
Figure S20. Changes of the chemical shift changes of ArH on PA[6] with addition of
OTA. The red solid line was obtained from the non-linear curve-fitting using Eq. 1.

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a) 6.68
6.680 b) 6.80
6.80

6.675 6.78

6.67
6.670 6.76
6.76

6.665 6.74

δ (ppm)
δ (ppm)

6.660
6.66 6.72
6.72

6.655 6.70

6.650
6.65 6.68
6.68

6.645 6.66

6.640
6.64 6.64
6.64

0
0 1 2
2.0 3 4 0 1 2
2.0 3 4
1.0 3.0 4.0 0 1.0 3.0 4.0
[Guest]/[Host] [Guest]/[Host]
Figure S21. Molar ratio plot for the binding of OTA with (a) PA[9], (b) PA[10] in
chloroform-d at 25 °C.

0.035
0.035

0.030
0.030

0.025
0.025
Δδ (ppm)

0.020
0.020 R2 = 0.971
Ka = 3.0 (±0.3) × 10 2 M -1
0.015
0.015

0.010
0.010

0.005
0.005

0.000
0
0.000 0.001 0.002 0.003 0.004
0 0.001 0.002 0.003 0.004
[OTA] (M)
Figure S22. Changes of the chemical shift changes of ArH on PA[9] with addition of
OTA. The red solid line was obtained from the non-linear curve-fitting using Eq. 1.

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0.16
0.16

0.14

0.12
0.12

0.10
R2 = 0.984
0.08
0.08 K1 = 7.2 (±0.2) × 10 2 M -1
2
K2 = 5.5 (±0.2) × 10 M -1
0.06

0.04
0.04

0.02

0.00
0
0 1 2 3 4
0 0.001 0.002 0.003 0.004
[OTA] (M)
Figure S23. Changes of the chemical shift changes of ArH on PA[10] with addition of
OTA. The red solid line was obtained from the non-linear curve-fitting using Eq. 2.

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7. HR ESI-MS experiments:

a) 2.50
1447.7855
2.00 [PA[8] ⊃ Na] +
Intens.(×10 5)

1.50

1.00

0.50

0
1000 1500 2000 2500
m/z
b) 2.50
1776.1029
2.00 [PA[9] ⊃ OTA-PF6 ] +
Intens.(×10 5)

1.50

1.00

0.50

0
1500 2000 2500
m/z
c) 1.25
1954.2049
[PA[10] ⊃ OTA-PF6 ] +
1.00
Intens.(×10 5 )

0.75

0.50

0.25 [PA[10] ⊃ 2OTA-PF 6 ]+

2271.3746
0
1500 2000 2500
m/z
Figure S24. ESI-MS of the mixture of OTA (3.0 mM) with (a) PA[8] (0.5 mM), (b)
PA[9] (0.5 mM) and (c) PA[10] (0.5 mM) in chloroform.

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8. 2D 1H NMR NOESY experiment:

Hb
Hc
O
CH2
Hd H7 H5 H3 H1 Hα
+
Ha N PF6-
10 H8 H6 H4 H2
O

PA[10] OTA
2 6
H1 H -H

Hα H8
7
+ H2O H

Hc

Hd
Hb

Ha

Figure S25. 2D 1H NMR NOESY spectrum (mixing time = 500 ms) of PA[10] (6.0
mM) and OTA (48 mM) in CDCl3 at 298 K.

9. References:
(1) Tao, H. Q.; Cao, D. R.; Liu, L. Z.; Kou, Y. H.; Wang, L. Y.; Meier, H. Sci. China:
Chem. 2012, 55, 223-228.
(2) Thordarson, P. Chem. Soc. Rev. 2011, 40, 1305-1323.

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