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Synthesis, Reaction, and Optical Properties of Cyclic Oligomers bearing 9,10-Diphenylanthracene Based on an Aromatic Tertiary Amide Unit Ryohei Yamakado,a Shin-ichi Matsuoka,a Masato Suzuki,a Daisuke Takeuchi,b Hyuma Masu,c Isao Azumaya,d and Koji Takagia* a Department of Materials Science and Engineering, Nagoya Institute of Technology Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan b Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8503, Japan c Chemical Analysis Center, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan d Faculty of Pharmaceutical Sciences, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan
Contents 1. Synthesis of C3Aʹ, C4Aʹ, and 2 S2–S3 2. Copy of NMR spectra S4–S13 3. GPC profiles S14 4. MALDI-TOF MS S15–S16 5. UV and fluorescence spectra S17–S19
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S2
Scheme S1. Synthetic route to cyclic aromatic oligomers C3Aʹ and C4Aʹ.
C3Aʹ Yield, 25%. M.p. >300 ˚C. 1H NMR (δ, 600 MHz, ppm, CDCl3) 7.64 (d, J = 8.0 Hz, 6H), 7.54 (d, J = 8.9 Hz, 6H), 7.47 (d, J = 8.9 Hz, 6H ), 7.41 (d, J = 8.2 Hz, 6H), 7.39–7.36 (12H), 6.94 (m, 6H), 6.89 (m, 6H), 4.21 (t, J = 7.8 Hz, 6H), 1.95 (m, 6H), 1.14 (t, J = 7.7 Hz, 9H). 13C NMR
(δ, 150 MHz, ppm, CDCl3) 170.5, 143.0, 140.7, 136.8, 136.2, 136.1, 135.9, 131.9, 130.6, 130.0, 129.9, 128.9, 128.1, 126.5, 126.1, 125.5, 125.2, 51.6, 21.2, 11.5.
C4Aʹ Yield 10%. M.p. >300 ˚C. 1H NMR (δ, 600 MHz, ppm, CDCl3) 7.67 (d, J = 7.9 Hz, 6H), 7.60 (m, 6H), 7.57 (m, 6 H), 7.43 (d, J = 8.3 Hz, 6H), 7.41 (d, J = 8.3 Hz, 6H), 7.35 (d, J = 8.3 Hz, 6H), 7.15 (t, J = 7.0 Hz, 6H), 7.11 (t, J = 7.0 Hz, 6H), 4.17 (t, J = 7.4 Hz, 6H), 1.90 (m, 6H),
1.57 (m, 6H), 1.13 (t, J = 7.0 Hz, 9H). 13C NMR (δ, 150 MHz, ppm, CDCl3) Not available due to low solubility.
NPr O
n
N COOCH3
1' C3A' [n = 3 (25 %)]C4A' [n = 4 (10 %]
LiHMDS (1M THF soln.)
0 oC
Pr
H
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S3
Scheme S2. Synthetic route to model compound 2. Condition and reagents: i) Benzoylchloride, Pyridine, THF, reflux; (ii) N-Methylaniline, LiHMDS (1 M THF soln.), THF, 0 ˚C.
6 Compound 1ʹ was prepared as 1. To a solution of 1ʹ (222 mg/ 0.5 mmol) in pyridine (2 mL) and THF (2 mL) was added benzoylchloride (0.08 mL/ 0.6 mmol), and the system was heated to reflux overnight. The reaction mixture was poured into water, and an aqueous phase was extracted with DCM. The combined organic phase was washed with 1 M HCl. After drying over MgSO4, solvents were removed by the rotary evaporator. The crude product was purified by column chromatography (ethyl acetate/DCM = 1/3) to obtain yellow powder (250 mg, 91%).
M.p. 256–257 ˚C. 1H NMR (δ, 200 MHz, ppm, CDCl3) 8.28 (d, J = 8.6 Hz, 2H), 8.17 (d, J = 8.0 Hz, 2H), 7.71–7.27 (17H), 4.10–3.90 (5H), 1.83 (m, 2H), 1.08 (t, J = 7.0 Hz, 3H). 2 To a THF (5 mL) solution of 6 (250 mg/ 0.45 mmol) and N-methylaniline (0.08 mL/ 0.75 mmol) was added dropwise a 1.0 M THF solution of LiHMDS (1.0 mL), and the system was stirred for 10 h. After saturated aq. NH4Cl was added, an aqueous phase was extracted with DCM. A combined organic phase was dried over MgSO4 and solvents were removed by the rotary evaporator. The resulted solid was recrystallized with CHCl3/hexane to give yellow crystals (140 mg, 50%).
M.p. 329–330 ˚C. 1H NMR (δ, 200 MHz, ppm, CDCl3) 7.53 (d, J = 7.8 Hz, 2H), 7.51–7.46 (2H), 7.43 (d, J = 7.8 Hz, 2H), 7.37–7.21 (d, J = 7.9 Hz, 2H), 7.20 (d, J = 8.6 Hz, 2H), 4.06 (d, J
= 6.1 Hz, 2H), 3.61 (s, 3H), 1.07 (t, J = 6.1 Hz, 3H). 13C NMR (δ, 50 MHz, ppm, CDCl3) 170.7, 170.4, 144.9, 140.2, 136.6, 136.2, 131.9, 130.7, 129.5, 129.1, 128.7, 128.1, 127.7, 127.1, 126.7, 125.1, 38.3, 30.3, 21.2, 11.5.
N COOCH3
1'
Pr
HN COOCH3
6
Pr
O
Ph
NPr
O
PhN
O
CH3Ph
2
(i) (ii)
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2. Copy of NMR spectra
Figure S1. 1H NMR spectrum of 3 in CDCl3.
Figure S2. 13C NMR spectrum of 3 in CDCl3.
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Figure S3. 1H NMR spectrum of 4 in CDCl3.
Figure S4. 13C NMR spectrum of 4 in CDCl3.
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Figure S5. 1H NMR spectrum of 5 in CDCl3.
Figure S6. 13C NMR spectrum of 5 in CDCl3.
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Figure S7. 1H NMR spectrum of 1 in CDCl3.
Figure S8. 13C NMR spectrum of 1 in CDCl3.
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Figure S9. 1H NMR spectrum of C3A in CDCl3.
Figure S10. 13C NMR spectrum of C3A in CDCl3.
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Figure S11. H-H COSY of C3A in CDCl3 (aromatic region).
Figure S12. ROESY of C3A in CDCl3 (aromatic region).
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Figure S13. 1H NMR spectrum of C4A in CDCl3.
Figure S14. H-H COSY of C4A in CDCl3 (aromatic region).
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Figure S15. 1H NMR spectrum of HC3A in CDCl3.
Figure S16. H-H COSY of HC3A in CDCl3(aromatic region)
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S12
Figure S17. Variable-temperature 1H NMR spectra of C3A in CDCl3.
293 K
273 K
253 K
223 K
O
N C8H17
NC8H17
O
NOC8H17
fg
f'g'
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S13
Figure S18. 1H NMR spectrum of 2 in CDCl3.
Figure S19. 13C NMR spectrum of 2 in CDCl3.
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2. GPC profiles
Figure S20. GPC (THF) profiles of reaction mixture.
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3. MALDI-TOF MS
Figure S21. MALDI-TOF MS of C3A.
Figure S22. MALDI-TOF MS of C4A.
1 [1] SP-C05-00-001.tas Description: DPA_C3A_2
1450
.728
1451
.731
1452
.735
1453
.739
1410 1420 1430 1440 1450 1460 1470 1480 1490 m/z0.00
0.40
0.80
1.20
1.60
2.00
2.40
2.80
3.20
3.60
4.00
x105
Inte
nsi
ty
1 [1] SP-G03-00-001.tas Description: C4A
1933
.499
1934
.503
1935
.506
1900 1910 1920 1930 1940 1950 1960 1970 m/z
0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40
1.60
1.80
2.00
x104
Inte
nsi
ty
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Figure S23. MALDI-TOF MS of HC3A.
1 [1] SP-C03-00-001.tas Description: N_DPA_C3Ak
1406
.821
1407
.825
1408
.829
1409
.833
1384 1388 1392 1396 1400 1404 1408 1412 1416 1420 1424 1428 1432 m/z0.00
0.40
0.80
1.20
1.60
2.00
2.40
2.80
3.20
x105
Inte
nsi
ty
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4. UV and fluorescence spectra
Table S1. Detailed absorption and emission peak positions of C3A and 2 in DCM.
Compound λabs/nm ε/M-1cm-1 λem/nm Φa
C3A 377 52000 438 0.15 C4A 378 59900 439 0.06
2 376 14900 425 0.15 a Relative to quinine sulfate with Φfl=0.55 as the standard.
Figure S24. UV and fluorescence spectra of C3A in Cyclohexane (purple), THF (green), DCM (black), MeCN (orange), and MeOH (red) (10-5 M).
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Figure S25. UV and fluorescence spectra of C3A (blue line) and C4A (red line) in DCM (solid line, 10-5M) and solid-state (dashed line).
Figure S26. Solvent-dependent UV spectra of HC3A (10-5 M).
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Table S2. Detailed absorption and emission peak positions of HC3A in different solvents.
ET(30)
/kcal・mol-1
HC3A
λabs /nm
ε
/M-1cm-1 λem /nm
Stokes shift /cm-1
Φa
/%
CH 30.9 396 31000 449 2980.8 0.10 Hexane 31.0 395 27000 446 2894.9 0.10 Toluene 33.9 397 32500 464 3637.2 0.10 DOX 36.0 397 29200 472 4002.5 0.16 EtOAc 38.1 395 31700 488 4824.7 0.11 DCM 40.7 397 31300 489 4739.0 0.08 Acetone 42.2 396 31500 509 5606.2 0.09 DMAc 42.9 397 30500 525 6141.3 0.11 DMF 43.2 398 29400 527 6150.3 0.09 DMSO 45.1 399 23000 543 6646.5 0.10
a Relative to quinine sulfate with Φfl=0.55 as the standard.
Figure S27. Changes in UV and fluorescence spectra of HC3A in DCM upon the addition of TFA and TEA; HC3A (red solid line), HC3A/TFA = 1/100 (blue solid line), and HC3A/TFA/TEA = 1/100/200 (red broken line).
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