electronic supplementary information supplementary information triptycene ... synthesis and...

19
S1 Electronic Supplementary Information Triptycene-derived calix[6]arenes: synthesis, structure and tubular assemblies in the solid state Xiao-Hong Tian, a,b Xiang Hao, a Tong-Ling Liang a and Chuan-Feng Chen* a a Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. b Graduate School, Chinese Academy of Sciences, Beijing 100049, China E-mail: [email protected] Content 1. Synthesis and characterization data of macrocycles 1 and 2 -----------------------S2 2. Copies of 1 H NMR and 13 C NMR spectra of new compounds --------------------S6 3. 1 H- 1 H COSY and 13 C- 1 H COSY 2D NMR spectra of 1 and 2 -------------------S14 4. X-ray crystal structures and packing of 1 and 2 ------------------------------------S18 Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009

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Page 1: Electronic Supplementary Information Supplementary Information Triptycene ... Synthesis and characterization data of macrocycles 1 and ... mixture of 2, 7-dimethyl-1, 8- dihydroxy-9,

S1

Electronic Supplementary Information

Triptycene-derived calix[6]arenes: synthesis, structure and tubular

assemblies in the solid state

Xiao-Hong Tian,a,b Xiang Hao,a Tong-Ling Lianga and Chuan-Feng Chen*a

aBeijing National Laboratory for Molecular Sciences, CAS Key Laboratory of

Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of

Sciences, Beijing 100190, China. bGraduate School, Chinese Academy of Sciences,

Beijing 100049, China

E-mail: [email protected]

Content

1. Synthesis and characterization data of macrocycles 1 and 2 -----------------------S2

2. Copies of 1H NMR and 13C NMR spectra of new compounds --------------------S6

3. 1H-1H COSY and 13C-1H COSY 2D NMR spectra of 1 and 2 -------------------S14

4. X-ray crystal structures and packing of 1 and 2 ------------------------------------S18

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009

Page 2: Electronic Supplementary Information Supplementary Information Triptycene ... Synthesis and characterization data of macrocycles 1 and ... mixture of 2, 7-dimethyl-1, 8- dihydroxy-9,

S2

1. Synthesis and characterization data of macrocycles 1 and 2

H3CO H3COHOH2C

CH2OH

KMnO4

66%

CH3OH, H+

reflux, 93% 95%

H3CO H3COH3CO2C

CO2CH3

H3CO H3COHO2C

CO2H

NaBH4

O

O OHOH

O

O OCH3OCH3

88%

Zn powder

OCH3OCH3

85%

H3CO H3CO

4 5 6

7 8

9 3

(CH3)2SO4

92%10% NaOH

benzenediazonium carboxylate

2, 7-Dimethyl-1, 8-dimethoxy-9, 10-anthracenedione (5). To a vigorously stirred

mixture of 2, 7-dimethyl-1, 8- dihydroxy-9, 10-anthracenedione 4S1 (3.0 g, 11.1 mmol)

and K2CO3 (12.3 g, 89.1 mmol) in acetone (100 mL) was added dimethylsulfate (8.4

mL, 88.8 mmol). The reaction mixture was refluxed for 24 h. The solvent was

evaporated under reduced pressure, and then concentrated ammonia solution was

added. The solution was stirred for 3 h at r.t. and filtered. The residue was purified by

column chromatography on silica gel with petroleum ether/EtOAc (4:1) as eluent to

afford 5 (2.9 g, 88 %) as a yellow solid. Mp: 160-162 °C. 1H NMR (300 MHz,

CDCl3): δ 2.42 (s, 6H), 3.95 (s, 6H), 7.53 (d, J = 7.8 Hz, 2H), 7.94 (d, J = 7.8 Hz, 2H). 13C NMR (75 MHz, CDCl3): δ 16.7, 61.6, 122.5, 127.7, 133.1, 135.6, 140.4, 158.4,

183.0, 183.6. EI-MS: 321 [M+Na]+. Anal. calcd. for C18H16O4: C 72.96, H 5.44;

found: C 72.64, H 5.56.

2, 7-Dimethyl-1, 8-dimethoxyanthracene (6). To a 10% NaOH solution (150 mL) of

compound 5 (2.9 g, 9.7 mmol) was added zinc powder (3.3 g, 49.8 mmol). The

mixture was stirred for 4 h at 120 °C, cooled to room temperature and then filtered.

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009

Page 3: Electronic Supplementary Information Supplementary Information Triptycene ... Synthesis and characterization data of macrocycles 1 and ... mixture of 2, 7-dimethyl-1, 8- dihydroxy-9,

S3

The filtered cake was washed with CH2Cl2. The organic solution was concentrated,

and the residue was subjected to chromatography on silica gel with petroleum ether/

CH2Cl2 (4:1) as eluent to give compound 6 (2.4 g, 92 %) as a light-yellow crystals.

Mp: 152-153 °C. 1H NMR (300 MHz, CDCl3): δ 2.49 (s, 6H), 4.01 (s, 6H), 7.26 (d, J

= 8.8 Hz, 2H), 7.67 (d, J = 8.8 Hz, 2H), 8.34 (s, 1H), 8.85 (s, 1H). 13C NMR (75 MHz,

CDCl3): δ 16.0, 61.1, 114.3, 123.9, 124.6, 126.4, 126.9, 129.2, 131.8, 153.3. EI-MS:

267 [M+H]+, 289 [M+Na]+. Anal. calcd. for C18H18O2: C 81.17, H 6.81; found: C

81.12, H 6.87.

2, 7-Dimethyl-1, 8-dimethoxytriptycene (7). To a refluxing solution of compound 6

(2.4 g, 9.0 mmol) in 1,2-dichloroethane (100 mL) and 1, 2-epoxypropane (10 mL)

was added portionwise benzenediazonium carboxylate (5.4 g, 36.0 mmol) over 24 h.

The reaction mixture was concentrated under reduced pressure and then purified by

column chromatography (petroleum ether/CH2Cl2 4:1) to give 7 (2.6 g, 85 %) as a

white solid. Mp: 156-158 °C. 1H NMR (300 MHz, CDCl3): δ 2.18 (s, 6H), 3.87 (s,

6H), 5.33 (s, 1H), 6.15 (s, 1H), 6.78 (d, J = 7.4 Hz, 2H), 6.98 (m, 2H), 7.04 (d, J = 7.4

Hz, 2H), 7.30– 7.73 (m, 2H).13C NMR (75 MHz, CDCl3): δ 15.7, 42.3, 53.8, 61.4,

119.2, 123.5, 123.6, 125.1, 127.4, 127.9, 137.0, 144.8, 145.8, 146.4, 153.7. EI-MS:

365 [M+Na]+. Anal. calcd. for C24H22O2: C 84.18, H 6.48; found: C 83.97, H 6.55.

1, 8-Dimethoxytriptycene-2, 7-dicarboxylic acid (8). To a refluxing solution of

compound 7 (2.6 g, 7.7 mmol) in pyridine (60 mL) and H2O (20 mL) was added

portionwise KMnO4 (21.9 g, 138.6 mmol, 9 equiv per CH3 group) over 24 h. After

cooling to r.t., the reaction mixture was filtered and washed with 1 % NaOH solution.

The filtrate was evaporated, and then acidified to pH 1 with 6 N HCl. The suspension

was filtered, dried and further purified by recrystallization from methanol to afford 8

(2.1 g, 66 %) as a white solid. Mp: 254-256 °C. 1H NMR (300 MHz, CDCl3): δ 3.90

(s, 6H), 5.86 (s, 1H), 6.26 (s, 1H), 7.07 (m, 2H), 7.35 (d, J = 7.6 Hz, 2H), 7.45 (d, J =

7.6 Hz, 2H), 7.50 (m, 1H), 7.61 (m, 1H). 13C NMR (75 MHz, CDCl3): δ 52.7, 62.6,

119.6, 123.1, 123.8, 124.2, 125.5, 125.7, 128.6, 137.9, 143.7, 144.2, 150.8, 154.1,

166.8. EI-MS: 401 [M-H]+. Anal. calcd. for C24H22O2: C 71.64, H 4.51; found: C

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009

Page 4: Electronic Supplementary Information Supplementary Information Triptycene ... Synthesis and characterization data of macrocycles 1 and ... mixture of 2, 7-dimethyl-1, 8- dihydroxy-9,

S4

71.86, H 4.68.

1, 8-Dimethoxytriptycene-2, 7-dicarboxylic acid dimethyl ester (9). To a refluxing

solution of compound 8 (2.1 g, 5.2 mmol) in methanol (40 mL) was added SOCl2 (5.0

mL) dropwise. The mixture was refluxed for another 8 h. After the mixture was

cooled, the suspension was filtered to afford 9 (2.1 g, 93 %) as a white solid. Mp:

200-202 °C. 1H NMR (300 MHz, CDCl3): δ 3.85 (s, 6H), 3.99 (s, 6H), 5.49 (s, 1H),

6.33 (s, 1H), 7.03 (m, 2H), 7.20 (d, J = 7.7 Hz, 2H), 7.38–7.47 (m, 2H), 7.55 (d, J =

7.7 Hz, 2H). 13C NMR (75 MHz, CDCl3): δ 41.7, 52.0, 54.4, 63.1, 119.5, 122.0, 124.0,

124.1, 125.7, 125.9, 129.4, 138.6, 143.8, 144.2, 151.5, 155.2, 166.2. EI-MS: m/z 431

[M+H]+, 453 [M+Na]+. Anal. calcd. for C26H22O6: C 72.55, H 5.15; found: C 72. 21,

H 5.21.

2, 6-Dihydroxymethyl-1, 8-dimethoxytriptycene (3). To a solution of 9 (2.1 g,

4.9mmol) in THF was added sodium borohydride (1.9 g, 49mmol). The mixture was

stirred for 15 min at refluxing temperature. Methanol (8 mL) was then added

dropwise. The mixture was refluxed for another 3 h. After cooling to r.t., 3 N HCl was

added to quench the reaction and extracted with CH2Cl2. The organic phase was dried

and concentrated to give pure alcohol 3 (1.7 g, 95 %) as a white solid. Mp: 170-171

°C. 1H NMR (300 MHz, CDCl3): δ 1.92 (s, 2H), 3.96 (s, 6H), 4.61 (s, 4H), 5.41 (s,

1H), 6.15 (s, 1H), 6.97 (d, J = 7.4 Hz, 2H), 7.02 (m, 2H), 7.14 (d, J = 7.4 Hz, 2H),

7.30–7.52 (m, 2H). 13C NMR (75 MHz, CDCl3): δ 42.2, 54.0, 61.3, 62.7, 119.7, 123.5,

123.9, 125.5, 126.1, 131.1, 137.0, 144.0, 145.6, 147.7, 153.5. EI-MS: m/z 397

[M+Na]+. Anal. calcd. for C24H22O4: C 76.99, H 5.92; found: C 76.64, H 5.94.

Reference:

S1. C. Marschalk, F. Koenig, N. Ouroussoff, Bull. Soc. Chim. Fr., 1936, 5,

1545–1568.

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009

Page 5: Electronic Supplementary Information Supplementary Information Triptycene ... Synthesis and characterization data of macrocycles 1 and ... mixture of 2, 7-dimethyl-1, 8- dihydroxy-9,

S5

+

OH

p-TsOH OH

OH

+OMe

OMe

OH

OMe

OMe OMe

OMe

OH

OMe

OMe3

1 2

Cl

Cl

1 and 2. To a solution of catalytic amount of TsOH in o-dichlorobenzene (60 mL)

was slowly added at 100 °C a solution of 3 (0.374 g, 1 mmol) and p-tert-butylphenol

(0.15 g, 1 mmol) in o-dichlorobenzene (120 mL) under argon atmosphere. After 24 h

an additional quantity of p-tert-butylphenol (0.15g, 1 mmol) was added and the

mixture heated for an additional 24 h. The dark resolution was evaporated in vacuum,

and then the mixture was separated by column chromatography over silica gel (eluent:

1:10 ethyl acetate/petroleum ether) to afford 1 (0.19 g, 19%) and 2 (0.17 g, 17%). 1

and 2 could be further crystallized from CH2Cl2/petroleum ether. 1. Mp: 300 > °C. 1H

NMR (300 MHz, CDCl3): δ 1.30 (s, 18H), 3.35 (d, J = 15.3 Hz, 4H), 3.91 (s, 12H),

4.25 (d, J = 15.3 Hz, 4H), 5.24 (s, 2H), 5.97 (s, 2H), 6.09 (s, 2H), 6.64 (d, J = 7.6 Hz,

4H), 6.88–6.97 (m, 8H), 7.08 (s, 4H), 7.28–7.40 (m, 4H). 13C NMR (75 MHz, CDCl3):

δ 29.9, 31.7, 33.9, 42.6, 53.7, 62.5, 119.9, 123.4, 123.6, 125.1, 125.2, 125.4, 126.5,

127.2, 130.0, 136.7, 141.9, 144.9, 145.8, 146.6, 150.2, 152.6. MALDI-TOF MS: m/z

999 [M+Na]+, 1015 [M+K]+. Anal. Calcd for C68H64O6·1.5CH2Cl2·0.5H2O: C 74.96,

H 6.15; found: C 74.97, H 6.21. 2. Mp: > 300 °C. 1H NMR (300 MHz, CDCl3): δ 1.22

(s, 18H), 3.20 (s, 12H), 3.68 (d, J = 14.5 Hz, 4H), 3.87 (d, J = 14.5 Hz, 4H), 5.34 (s,

2H), 5.86 (s, 2H), 6.00 (s, 2H), 6.97 (m, 8H), 7.16–7.02 (m, 8H), 7.30–7.40 (m, 4H). 13C NMR (75 MHz, CDCl3): δ 31.6, 32.6, 34.0, 42.5, 53.9, 61.9, 119.4, 123.4, 125.1,

125.3, 126.1, 127.3, 128.0, 130.9, 136.8, 143.0, 144.6, 146.3, 146.5, 150.5, 153.2.

MALDI-TOF MS: m/z 999 [M+Na]+, 1015 [M+K]+. Anal. Calcd for

C68H64O6·0.5H2O: C 74.66, H 6.12; found: C 74.84, H 6.36.

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009

Page 6: Electronic Supplementary Information Supplementary Information Triptycene ... Synthesis and characterization data of macrocycles 1 and ... mixture of 2, 7-dimethyl-1, 8- dihydroxy-9,

S6

2. Copies of 1H NMR and 13C NMR spectra of new compounds

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.56.

12

6.00

1.92

1.94

0.02

50

2.39

18

3.95

22

7.24

347.

5150

7.92

087.

9469

O

O OCH3OCH3

Figure S1. 1H NMR spectrum (CDCl3) of 5.

O

O OCH3OCH3

0102030405060708090110130150170190

16.7

309

61.6

284

76.5

803

77.0

036

77.4

273

122.

5164

127.

6959

133.

1156

140.

4462

158.

4090

183.

0028

183.

5410

Figure S2. 13C NMR spectrum (CDCl3) of 5.

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009

Page 7: Electronic Supplementary Information Supplementary Information Triptycene ... Synthesis and characterization data of macrocycles 1 and ... mixture of 2, 7-dimethyl-1, 8- dihydroxy-9,

S7

0.01.02.03.04.05.06.07.08.09.010.0

5.96

5.99

2.32

1.97

0.99

1.00

-0.0

004

2.48

95

3.98

94

7.24

537.

2746

7.66

037.

6890

8.34

24

8.84

73

OCH3OCH3

Figure S3. 1H NMR spectrum (CDCl3) of 6.

OCH3OCH3

-100102030405060708090100110120130140150160170

15.9

752

61.0

931

76.5

704

76.9

937

77.4

168

114.

2817

123.

8916

124.

6116

126.

4271

126.

8765

129.

2179

131.

7831

153.

2670

Figure S4. 13C NMR spectrum (CDCl3) of 6.

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009

Page 8: Electronic Supplementary Information Supplementary Information Triptycene ... Synthesis and characterization data of macrocycles 1 and ... mixture of 2, 7-dimethyl-1, 8- dihydroxy-9,

S8

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0

5.92

5.83

1.00

1.03

1.96

1.93

1.81

1.01

0.91

-0.0

004

2.18

91

3.87

08

5.32

85

6.14

67

6.76

596.

9647

7.02

397.

2500

7.34

607.

4056

7.42

24

H3CO H3COH3C

CH3

Figure S5. 1H NMR spectrum (CDCl3) of 7.

H3CO H3COH3C

CH3

-100102030405060708090100110120130140150160

15.7

905

42.3

718

53.9

013

61.5

259

76.7

036

77.1

270

77.5

506

119.

3151

123.

6095

123.

6635

127.

4840

137.

1192

144.

8596

153.

7676

Figure S6. 13C NMR spectrum (CDCl3) of 7.

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009

Page 9: Electronic Supplementary Information Supplementary Information Triptycene ... Synthesis and characterization data of macrocycles 1 and ... mixture of 2, 7-dimethyl-1, 8- dihydroxy-9,

S9

0.52.03.55.06.58.09.511.513.5

5.27

1.00

1.00

1.99

1.92

1.74

0.99

1.06

1.93

-0.0

310

2.50

23

3.32

36

3.88

58

5.85

206.

2100

7.32

207.

3476

7.42

547.

4508

7.49

117.

5011

7.58

687.

5977

12.7

931

H3CO H3COHO2C

CO2H

Figure S7. 1H NMR spectrum (CDCl3) of 8.

H3CO H3COHO2C

CO2H

-100102030405060708090110130150170

38.6

882

38.9

680

39.2

455

39.5

234

39.8

017

40.0

804

40.3

590

40.9

340

52.5

196

62.6

458

119.

5662

123.

0778

123.

7963

124.

2143

125.

5918

128.

5956

137.

8988

143.

6528

150.

8199

154.

1277

166.

7840

Figure S8. 1H NMR spectrum (CDCl3) of 8.

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009

Page 10: Electronic Supplementary Information Supplementary Information Triptycene ... Synthesis and characterization data of macrocycles 1 and ... mixture of 2, 7-dimethyl-1, 8- dihydroxy-9,

S10

H3CO H3COH3CO2C

CO2CH3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5

6.02

6.05

1.01

1.00

1.99

2.04

1.04

1.06

1.86

-0.0

246

3.85

623.

9907

5.48

99

6.33

12

7.02

687.

0420

7.05

547.

1957

7.22

137.

2524

7.38

727.

3999

7.53

41

Figure S9. 13C NMR spectrum (CDCl3) of 9.

H3CO H3COH3CO2C

CO2CH3

-100102030405060708090110130150170

41.6

940

52.0

342

54.4

664

63.1

141

76.5

805

77.0

038

77.4

272

119.

4614

122.

0076

123.

9452

124.

0721

125.

6691

125.

9026

129.

3810

138.

5422

143.

7808

144.

2016

151.

4808

155.

2262

166.

1805

Figure S10. 13C NMR spectrum (CDCl3) of 9.

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009

Page 11: Electronic Supplementary Information Supplementary Information Triptycene ... Synthesis and characterization data of macrocycles 1 and ... mixture of 2, 7-dimethyl-1, 8- dihydroxy-9,

S11

H3CO H3COHOH2C

CH2OH

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0

2.47

6.18

4.29

1.17

1.11

1.95

1.88

1.93

1.00

1.00

-0.0

005

1.92

17

3.93

97

4.61

02

5.40

79

6.14

58

6.95

757.

0049

7.02

347.

1311

7.24

917.

3808

7.39

997.

4345

Figure S11. 1H NMR spectrum (CDCl3) of 3

H3CO H3COHOH2C

CH2OH

-100102030405060708090100110120130140150160170

42.1

649

53.9

886

61.3

328

62.7

168

76.5

805

77.0

042

77.4

277

119.

7481

123.

5391

123.

8555

125.

4624

126.

1337

131.

1010

137.

0131

143.

9776

153.

4555

Figure S12. 13C NMR spectrum (CDCl3) of 3

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009

Page 12: Electronic Supplementary Information Supplementary Information Triptycene ... Synthesis and characterization data of macrocycles 1 and ... mixture of 2, 7-dimethyl-1, 8- dihydroxy-9,

S12

OHOMe

OMe OMe

OMe

OH

-1.00.01.02.03.04.05.06.07.08.09.0

16.7

8

3.21

11.1

43.

51

1.66

1.48

1.71

3.26

6.35

3.22

2.23

1.92

0.00

32

1.30

451.

5349

3.32

543.

3764

3.91

424.

2252

4.27

60

5.23

99

5.97

396.

0927

6.62

826.

6535

6.92

016.

9452

6.96

697.

0779

7.25

337.

2680

7.28

097.

2959

7.38

63

7.40

14

Figure S3. 1H NMR spectrum (CDCl3) of 1

OHOMe

OMe OMe

OMe

OH

Figure S14. 13C NMR spectrum (CDCl3) of 1.

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009

Page 13: Electronic Supplementary Information Supplementary Information Triptycene ... Synthesis and characterization data of macrocycles 1 and ... mixture of 2, 7-dimethyl-1, 8- dihydroxy-9,

S13

OH

OHOMe

OMe

OMe

OMe

Figure S15. 1H NMR spectrum (CDCl3) of 2

OH

OHOMe

OMe

OMe

OMe

0102030405060708090100110120130140150160

31.6

144

32.6

001

33.9

988

42.5

132

53.8

536

61.9

179

76.5

863

77.0

094

77.4

335

119.

4160

123.

3961

126.

1145

136.

8410

142.

9874

150.

4617

153.

2900

Figure S16. 13C NMR spectrum (CDCl3) of 2.

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009

Page 14: Electronic Supplementary Information Supplementary Information Triptycene ... Synthesis and characterization data of macrocycles 1 and ... mixture of 2, 7-dimethyl-1, 8- dihydroxy-9,

S14

3. 1H-1H COSY and 13C-1H COSY 2D NMR spectra of 1 and 2

ppm

3.54.04.55.05.56.06.57.07.58.0 ppm

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

8.0

OH

OMe

OMe OMe

OMe

OH

OMe

Ha

Hb

OHHa Hb

Hc

Hc'

Hc' Hc

Figure S17. 1H-1H COSY spectrum of 1.

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009

Page 15: Electronic Supplementary Information Supplementary Information Triptycene ... Synthesis and characterization data of macrocycles 1 and ... mixture of 2, 7-dimethyl-1, 8- dihydroxy-9,

S15

ppm

3.54.04.55.05.56.06.57.07.5 ppm

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

OH

OHOMe

OMe

OMe

OMe

Ha

Hb

Hc

Hc'

HOHbHa HcHc'

OMe

Figure S18. 1H-1H COSY spectrum of 2.

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009

Page 16: Electronic Supplementary Information Supplementary Information Triptycene ... Synthesis and characterization data of macrocycles 1 and ... mixture of 2, 7-dimethyl-1, 8- dihydroxy-9,

S16

OH

OMe

OMe OMe

OMe

OH

ppm

3.54.04.55.05.56.06.5 ppm

70

60

50

40

30

20

10

Figure S19. 13C-1H COSY spectrum of 1.

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OH

OHOMe

OMe

OMe

OMe

ppm

3.54.04.55.05.56.06.5 ppm

20

30

40

50

60

70

Figure S20. 13C-1H COSY spectrum of 2.

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4. X-ray crystal structures and packing of 1 and 2

The X-ray measurements were carried on a Saturn724+ CCD diffractometer with graphite-monochromator Mo-Kα radiation (λ = 0.71073 Å) at 173 K. Intensities were collected using CrystalClear (Rigaku Inc., 2008) technique and absorption effects were collected using the multi-scan technique. The structure of 1 was solved by direct methods and refined by a full matrix least squares technique based on F2 using SHELXL 97 program. The structure of 2 was solved using SHELXS-97 (Sheldrick, 1990) program and refined by a full matrix least squares technique based on F2 using SHELXL 97 program. Application of the restraints is for confining the thermal vibration parameters of the disordered solvent molecules, which can make them be isotropic. Because highly disordered solvent molecules were difficult to be determined, they were deleted with SQUEEZE program in the crystal structure of 1. For 2, the high R-factor and weighted R-factor might be mainly due to the solvent molecules which haven’t been treated with SQUEEZE program.

Figure S21. A 3D microporous structure of 1 viewed along the b-axis. Solvent molecules and hydrogen atoms were omitted for clarity.

Figure S22. View of the non-covalent interactions between CH2Cl2 molecules and macrocycle 2 during the formation of the organic tube. Other solvent molecules and hydrogen atoms not involved in the interactions are omitted for clarity.

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Figure S23. Packing of 2. View of a 2D layer structure. Dashed lines denote the non-covalent interactions between the CH2Cl2 molecule and its adjacent macrocycles.

Figure S24. Packing of 2. View of the 3D microporous structure (a) without the solvents, and (b) with the solvents situated in the different channels along the a-axis. Hydrogen atoms are omitted for clarity.

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009