chem f700830 s - wiley-vch · 40 (n-bu) 2n o o on(n-bu) 2 18 13c nmr (125mhz, cdcl3): £_13.55,...

Supporting Information

© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2008

1

Syntheses of Ladder-Type Oligonaphthalene Derivatives and Their

Photophysical and Electrochemical Properties

Jun-Chun Chen, Tse-Shi Lee, Chih-Hsiu Lin*

2

Supporting Information Table of Contents

1H and 13C spectra of compound 14……………………………..…………………..3-4 1H and 13C spectra of compound 1..…………………………..……………………..5-6 1H and 13C spectra of compound 2……..……………………..……………………..7-8 1H and 13C spectra of compound 3………..………………..……………………....9-10 1H and 13C spectra of compound 4…………...…………….……………………..11-12 1H and 13C spectra of compound 5…………..…………..………………………..13-14 1H and 13C spectra of compound 6……………..………..………………..………15-16 1H and 13C spectra of compound 7……………………..……………....…………17-18 1H and 13C spectra of compound 8’……….…………….…………..……………19-20 1H and 13C spectra of compound 8………..……………..…………………..……21-22 1H and 13C spectra of compound 9………..……………..……………..…………23-24 1H and 13C spectra of compound 10……………………..………………..………25-26 1H and 13C spectra of compound 11……………………..……………………..…27-28 1H and 13C spectra of compound 12…………………..…………………..………29-30 1H and 13C spectra of compound 13……………………..…..……………………31-32 1H and 13C spectra of compound 15……………………..……….…….…………33-34 1H and 13C spectra of compound 16………………………..………..……………35-36 1H and 13C spectra of compound 18………………………..……………………..37-38 1H and 13C spectra of compound 17……………………..…………………..……39-40 1H and 13C spectra of compound 19………………………..………………..……41-42 13C spectra of compound 8, 16, 17 in amid carbon region……….…………………..43 13C spectra of compound 8, 16, 17 in sp3 quaternary carbon region……….………..44 13C spectra of compound 8, 16, 17 in aromatic region…………………..….………..45 13C spectra of compound 9, 18, 19 in sp3 methine carbon region………….………..46 13C spectra of compound 9, 18, 19 in amid carbon region………………….………..47 13C spectra of compound 9, 18, 19 in aromatic region……………………...………..48 1H and 13C spectra of compound 23…………………………..………………..…49-50 1H and 13C spectra of compound 20…………………………..……………..……51-52 1H and 13C spectra of compound 21…………………………..……………..……53-54 1H and 13C spectra of compound 22………………………..………………..……55-56 1H and 13C spectra of compound 24………………………..………………..……57-58

3

1H and 13C spectra of compound 24’……….…………………...………..………59-60 1H and 13C spectra of compound 25 (impure)... ..………………...………………61-62 1H and 13C spectra of compounds in the model studies………..…………………63-85

Cyclic voltammetry results of compounds 2, 4, 9, 12……………………...……..86-87 1H UV-Vis and fluorescence spectra of compound 2, 4 and model

compounds……………………………………………..…………………………88-89

4

O N

O 14O

5

O N

O OMe 14

6

OMe

N(n-Bu)2O

1

7

OMe

N(n-Bu)2O

1

8

O

N(n-Bu)2

2

9

O

N(n-Bu)2

2

10

N(n-Bu)2O

OMe

3

11

N(n-Bu)2O

OMe

3

12

4

O N(n-Bu)2

13

4

O N(n-Bu)2

CF3

OMe

5

15

CF3

OMe

5

CF3

6

16

17

CF3

6

18

O

O O

O

N(n-Bu)2

(n-Bu)2N

7

19

O

O O

O

N(n-Bu)2

(n-Bu)2N

7

20

O N(n-Bu)2

O(n-Bu)2N

OH

OH

8'

21

O N(n-Bu)2

O(n-Bu)2N

OH

OH

8'

22

O N(n-Bu)2

O(n-Bu)2N

OMe

OMe

8

IR (KBr) £h (cm-1): 2944, 2868, 1631, 1461, 1432, 1082, 816, 742, 481. 1H NMR (500MHz, CDCl3): £_0.69~1.58 (m, 28 H), 3.15 (s, 6H), 3.15~3.45 (m, 8 H), 7.30 (d, J = 8.5 Hz, 4 H), 7.31~7.48 (m, 8H), 7.55 (d, J = 8.5 Hz, 4 H), 7.70~7.97 (m, 8 H), 7.98 (d, J = 9.5Hz, 4 H).

23

O N(n-Bu)2

O(n-Bu)2N

OMe

OMe

8

13C NMR (100MHz, CDCl3): £_13.46, 13.90, 19.60, 20.26, 29.67, 30.70, 44.45, 48.66, 52.44, 87.23, 126.08, 126.22,126.95, 127.22, 127.42, 127.46, 127.61, 128.09, 128.38, 128.77, 131.84, 132.43, 132.81, 136.05, 140.64, 141.31, 144.60, 171.39.

24

O N(n-Bu)2

O(n-Bu)2N

9

IR (KBr) £h(cm-1): 2957, 2927, 2864, 1631, 1465, 1428, 809, 750. 1H NMR (400MHz, CDCl3): £_0.75~1.58 (m,28 H), 3.20~3.44 (m, 8H), 5.25 (s, 2H), 7.17 (m, J = 8Hz, 4 H), 7.24~7.29 (m, 4 H), 7.45~7.60 (m, 8 H), 7.85(d, J = 8 Hz, 2 H), 7.98 (dd, J = 1.2 Hz, J = 8 Hz, 2 H),8.62~8.65 (m, 2H), 8.76 (d, J = 8 Hz, 2 H).

25

O N(n-Bu)2

O(n-Bu)2N

9

13C NMR (125MHz, CDCl3): £_13.55, 13.89, 19.67, 20.27,29.69, 30.75, 44.54, 48.73, 55.61, 121.33, 121.43, 122.87, 125.33, 126.81, 126.85, 127.06, 127.13, 128.45, 128.59,128.63, 128.89, 129.95, 134.23, 136.16, 137.84, 137.92,138.25, 138.36, 141.39, 146.46, 147.38, 147.50, 171.48.

26

O

O

O

O

N(n-Bu)2

(n-Bu)2N

10

27

O

O

O

O

N(n-Bu)2

(n-Bu)2N

10

28

OMe

MeO

O

ON(n-Bu)2

(n-Bu)2N 11

IR (KBr) £h(cm-1): 2959, 2929, 2870, 1631, 1461, 1428, 1070, 787, 731. 1HNMR (400MHz, CDCl3): £_0.57~1.57 (m, 28 H), 3.07 (m, bs, 4 H), 3.23 (s, 3 H), 3.24 (s, 3 H), 3.42 (m, bs, 4 H), 6.94~6.99 (m, 2 H), 7.10 (m, 1 H), 7.13~7.28(m, 10 H), 7.28~7.38 (m, 3 H), 7.48 (m, 4 H), 7.77 (m, 4 H), 8.26 (m, 1 H),8.33 (m, 1 H), 8.38~8.43 (m, 2 H).

29

OMe

MeO

O

ON(n-Bu)2

(n-Bu)2N 11

13C NMR (100MHz, CDCl3): £_13.34, 13.89, 19.51, 20.23, 29.66,30.64, 44.58, 48.66, 54.33, 91.48, 91.64, 123.51, 123.54, 124.29, 124.34, 125.19, 125.28, 125.80, 126.42, 128.30, 128.40, 128.49,128.61, 129.23, 131.87, 133.25, 134.65, 135.31, 138.73, 139.02,139.41, 139.77 (the four peaks between 138.73-139.77 areuncommonly broad) 144.98, 145.16, 171.49.

30

O N(n-Bu)2

O N(n-Bu)2

12

IR (KBr) (cm-1) 2957, 2927, 2866, 1628, 1461, 1424, 812, 742. 1H NMR (500MHz, CDCl3):£_0.58~1.54 (m, 28 H), £_3.04~3.40

(m, 8 H), 5.64 (s, 1 H), 5.73 (s, 1 H), 7.21~7.34 (m, 9 H),7.82~8.00 (m, 15 H).

31

O N(n-Bu)2

O N(n-Bu)2

12

13C NMR (100MHz, CDCl3): £_13.42, 13.87, 19.57, 20.22, 29.68,30.62 44.64, 48.71, 53.40, 53.91, 118.24, 118.91, 118.98, 123.64, 124.60, 124.63, 125.05, 125.13, 126.45, 126.54, 127.20, 127.32,128.72, 128.77, 128.96, 129.04, 129.78, 129.84, 130.03, 130.05,133.25, 133.29, 135.55, 135.62, 138.44, 138.67, 139.15, 139.24,142.96, 143.11, 144.03, 145.39, 171.38, 171.41.

32

O N(n-Bu)2

OMe Br

13

33

O N(n-Bu)2

OMe Br

13

34

O

O

(n-Bu)2N

15

35

O

O

(n-Bu)2N

15

36

O N(n-Bu)2

MeO

O N(n-Bu)2

OMe

OMe

O(n-Bu)2N

16

IR (KBr) £h(cm-1): 2957, 2932, 2867, 2820, 1632, 1461, 1424, 1078, 812, 753. 1H NMR(400MHz, CDCl3):£_0.69~1.63 (m, 42 H), 3.15 (s, 9 H), 3.15~3.45 (m, 12 H), 7.31 (m, 6 H), 7.44~7.50 (m, 10 H), 7.55 (m, 6 H), 7.70~7.79 (m, 10 H), 7.97~7.99 (m, 6 H).

38

O N(n-Bu)2

MeO

O N(n-Bu)2

OMe

OMe

O(n-Bu)2N

16

13C NMR (100MHz, CDCl3):£_13.46, 13.90, 19.60, 20.25, 29.60, 30.69,44.46, 48.67, 52.44, 87.22, 126.08, 126.21, 126.93, 126.96, 127.17,127.23, 127.41, 127.44, 127.60, 128.08, 128.12, 128.38, 128.77, 131.83, 132.42, 132.80, 136.03, 136.06, 140.64, 141.22, 144.52, 144.59, 171.37, 171.40.

39

O(n-Bu)2N

O N(n-Bu)2O N(n-Bu)2

18

IR (KBr) £h(cm-1): 2957, 2929, 2867, 1630, 1461, 1424, 1102, 805, 742.1H NMR (400MHz, CDCl3): £_0.74~1.60 (m, 42 H), 3.17~3.44 (m, 12 H), 5.26 (s, 2 H), 5.33 (s, 1 H), 7.14~7.30 (m, 12 H), 7.49~7.56 (m, 11 H),7.85 (d, J = 8 Hz, 2 H), 7.98 (d, J = 8 Hz, 2 H), 8.67~8.69 (m, 3 H),8.77~8.79 (m, 2 H).

40

O(n-Bu)2N

O N(n-Bu)2O N(n-Bu)2

18

13C NMR (125MHz, CDCl3): £_13.55, 13.89, 19.65, 20.27, 29.68, 30.75, 44.52, 48.72, 55.60, 55.68, 121.47, 121.54, 121.56, 121.69, 121.71, 121.73, 121.79,121.83, 122.89, 125.29, 125.32, 126.82, 127.13, 127.15, 127.21, 128.46,128.56, 128.60, 128.68, 128.89, 129.84, 129.86, 129.91, 134.25, 136.15,136.23, 137.83, 137.87, 137.92, 138.29, 138.32, 138.38, 138.39, 138.42,138.46, 138.48, 141.34, 141.38, 146.49, 146.57, 146.67, 146.75, 146.79,147.38, 147.40, 147.44, 171.42, 171.49, 171.50.

41

O N(n-Bu)2

MeO

O N(n-Bu)2

MeO

OMe

O(n-Bu)2N

OMe

17O(n-Bu)2N

IR (KBr) £h(cm-1): 2957, 2931, 2869, 2812, 1630, 1461, 1424, 1078, 812, 728. 1H NMR(500MHz, CDCl3): £_0.69~1.65 (m, 56 H), 3.14 (s, 12 H), 3.14~3.45 (m, 16 H), 7.29~7.31 (m, 8 H), 7.44~7.55 (m, 20 H), 7.69~7.78 (m, 12 H), 7.96~7.98 (m, 8 H).

42

O N(n-Bu)2

MeO

O N(n-Bu)2

MeO

OMe

O(n-Bu)2N

OMe

17O(n-Bu)2N

13C NMR (100MHz, CDCl3): £_13.46, 13.90, 19.59, 20.25, 29.59, 30.68, 44.44,48.65, 52.43, 87.18, 87.20, 126.08, 126.21, 126.92, 126.94, 127.16, 127.19,127.23, 127.41, 127.60, 128.07, 128.11, 128.387, 128.74, 128.76, 131.81,132.41, 132.79, 136.03, 140.62, 141.19, 141.30, 144.53, 144.56, 171.35, 171.38.

43

O(n-Bu)2N

O N(n-Bu)2

O(n-Bu)2N

O N(n-Bu)2

19

IR (KBr)£h(cm-1): 2956, 2926, 2860, 1631, 1461, 1425, 1102, 805, 751. 1H NMR (400MHz, CDCl3): £_0.74~1.58 (m, 56 H), £_3.17~3.44 (m, 16 H), 5.26 (s, 2 H),5.33 (s, 2 H), 7.15~7.30 (m, 16 H), 7.48~7.59 (m, 12 H), 7.85 (d, J = 8 Hz, 2 H),7.98 (d, J = 8 Hz, 2 H), 8.69~8.79 (m, 8 H).

44

O(n-Bu)2N

O N(n-Bu)2

O(n-Bu)2N

O N(n-Bu)2

19

13C NMR (125MHz, CDCl3): £_13.53, 13.86, 19.63, 20.24, 29.65, 30.72, 44.48, 48.69, 55.58, 55.64, 121.48, 121.55, 121.70, 121.74, 121.85, 122.87, 125.30, 126.81,126.95, 127.12, 128.44, 128.57, 128.62, 128.65, 128.87, 129.71, 129.83, 129.86,134.22, 136.13, 136.18, 137.80, 137.85, 138.31, 138.36, 138.39, 138.42, 138.46,138.53, 141.30, 146.50, 146.69, 146.72, 146.79, 146.82, 147.38, 147.42, 171.38,171.41, 171.45, 171.47.

45

8R OMe

R OMe

16R OMe

R OMe

R OMe

17R OMe

R OMe RMeO

RMeO

R =o

N(n-Bu)2

46

8R OMe

R OMe

16R OMe

R OMe

R OMe

17R OMe

R OMe RMeO

RMeO

R =o

N(n-Bu)2

47

8R OMe

R OMe

R =o

N(n-Bu)2

16R OMe

R OMe

R OMe

48

R

R 9

R

R 18 R

R

R19

R

R

R =o

N(n-Bu)2

49

R =o

N(n-Bu)2

R

R 9

R

R 18 R

R

R19

R

R

50

R

R 9

R =o

N(n-Bu)2

51

O

F3C

23

52

O

F3C

23

O

O

CF3

F3C

20

53

O

O

CF3

F3C

20

54

55

OMe

OMe

CF3

CF3

21

(KBr) £h(cm-1) 3048, 2940, 1406, 1326, 1118, 1070, 1016,843, 779; 1H NMR (400MHz, CDCl3): £_3.22-3.24 (2¡Ñs, 6H), 6.98~7.03 (m, 2 H), 7.10~7.15 (m, 2 H), 7.18~7.30 (m,6 H), 7.34~7.40 (m, 2 H), 7.51 (d, J = 8.4 Hz, 4 H), 7.61 (br, 4 H), 7.78 (t, J = 8.4 Hz, 4 H), 8.23-8.28 (m, 2H), 8.38 (d, J= 8.5 Hz, 2 H)

56

OMe

OMe

CF3

CF3

21

13C NMR (100MHz, CDCl3): £_ 54.25, 91.38, 91.48, 122.77, 123.72, 123.76, 124.39, 124.45, 124.60, 124.64, 124.68, 125.35, 125.41,125.47, 128.07, 128.18, 128.29, 128.52, 128.69, 128.80, 128.84,129.23, 129.43, 131.58, 133.24, 134.75, 138.51(b), 138.79(b),139.48(b), 139.72(b), 147.86, 148.01

CF3

CF322

IR (KBr) £h (cm-1) 3048, 2923, 1617, 1324, 1164, 1123, 1067, 1018, 808; 1H NMR (400MHz,CDCl3): £_5.62 (s, 2 H), 7.30~7.44 (m, 12 H),7.74~7.94 (m, 12 H)

57

CF3

CF3

22

13C NMR (100MHz, CDCl3): £_53.46, 118.17,119.50, 123.33, 124.31, 125.19, 125.84, 125.87,

58

126.64, 129.02, 129.12, 129.16, 129.50, 129.79, 133.28, 138.58, 139.09, 143.67, 145.03, 146.00

59

CF3

CF3

CF3

OH HO

OH

24

IR (KBr) £h(cm-1) 2949, 2826, 1609, 1403, 1326, 1165,1123, 1068, 787; 1H NMR (400MHz, CDCl3): £_3.21~3.27 (m, 9 H), 6.98~7.23 (m, 12 H), 7.25~7.29 (m, 2 H), 7.33~7.38 (m, 2 H), 7.46~7.54 (m, 7 H), 7.59 (br,5 H), 7.74~7.81 (m, 4 H), 8.18~8.37 (m, 6 H)

60

OH HO

OH

CF3 CF3

CF3

24

13C NMR (100MHz, CDCl3):£_54.26, 54.46, 91.35, 91.48, 120.05, 122.76, 123.72,123.76, 124.00, 124.15, 124.38, 124.45, 124.65, 124.68, 125.34, 125.38, 125.47,127.46, 127.63, 128.06, 128.17, 128.25, 128.53, 128.69, 128.79, 128.85, 129.13,129.41, 131.57, 133.03, 133.24, 134.74, 138.77 (b), 139.48 (b), 139.71 (b), 147.85, 147.98, 148.05, 148.18

61

CF3 CF3

CF3

OMe MeO

OMe

24'

IR (KBr) £h(cm-1) 2949, 2826, 1609, 1403, 1326, 1165, 1123, 1068, 787; 1H NMR(400MHz, CDCl3): £_ 3.21~3.27 (m, 9 H), 6.98~7.23 (m, 12 H), 7.25~7.29 (m, 2 H), 7.33~7.38 (m, 2 H), 7.46~7.54 (m, 7 H), 7.59 (br, 5 H), 7.74~7.81 (m, 4 H),8.18~8.37 (m, 6 H)

62

CF3 CF3

CF3

OMe

MeOOMe

24'

13C NMR (100MHz, CDCl3):£_54.26, 54.46, 91.35, 91.48, 120.05, 122.76,123.72, 123.76, 124.00, 124.15, 124.38, 124.45, 124.65, 124.68, 125.34, 125.38, 125.47, 127.46, 127.63, 128.06, 128.17, 128.25, 128.53, 128.69, 128.79, 128.85, 129.13, 129.41, 131.57, 133.03, 133.24, 134.74, 138.77 (b), 139.48 (b), 139.71(b), 147.85, 147.98, 148.05, 148.18

63

CF3 CF3

CF3

25 (impure)

IR (KBr) £h (cm-1) 2927, 2855, 1324, 1165, 1124, 1067, 807, 746; 1H NMR (400MHz, CDCl3): £_ 5.45~5.75 (m, 3 H), 7.25~7.48 (m, 21 H), 7.67~7.96 (m, 21 H)

64

CF3 CF3

CF3

25 (impure)

13C NMR (100MHz, CDCl3): £_53.54, 53.68, 53.81, 118.18, 118.30,119.03, 119.12, 119.27, 122.92, 123.32, 123.39, 124.38, 124.49, 125.08, 125.23, 125.29, 125.98 (b), 126.69, 126.75, 127.24, 129.03, 129.15,129.24, 129.53, 129.65, 129.83, 133.35, 138.63, 138.69, 138.86,138.95,139.12, 143.69, 144.82, 144.95, 145.06, 145.20, 145.97, 146.19

65

OH

66

OH

69

OH

70

OH

73

OH

74

OH

77

OH

78

OH

79

16

81

OH

OMeMeO

82

OH

OMeMeO

83

OMeMeO OMeMeO

And

84

OH

OMeMeO

85

OH

OMeMeO

86

OMeMeO

87

OMeMeO

88

1.8 1.6 1.4 1.2 1.0 0.8 0.6

-6.0x10-5

-5.0x10-5

-4.0x10-5

-3.0x10-5

-2.0x10-5

-1.0x10-5

0.0

1.0x10-5

Potential ( V vs Ag/AgNO3)

Cur

rent

( A

)

1.8 1.6 1.4 1.2 1.0 0.8 0.6-1.0x10-4

-8.0x10-5

-6.0x10-5

-4.0x10-5

-2.0x10-5

0.0

Cur

rent

( A

)


O N

O N

O N

89

2.0 1.5 1.0 0.5-5.0x10-5

-4.0x10-5

-3.0x10-5

-2.0x10-5

-1.0x10-5

0.0

1.0x10-5


Cur

rent

( A

)

1.8 1.6 1.4 1.2 1.0 0.8 0.6-6.0x10-5

-5.0x10-5

-4.0x10-5

-3.0x10-5

-2.0x10-5

-1.0x10-5

0.0

1.0x10-5

Cur

rent

( A

)


O N

ON

O N

90

250 300 350 400 450 500-0.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2A

borb

ance

(AU

)

Wavelength (nm)

4a 4b 4 naphthalene

250 300 350 400 450 500 550 600-0.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

Inte

nsity

(nor

mal

ized

)

Wavelength(nm)

4a 4b 4

4a 4b4

O N

4a 4b4

O N

91

250 300 350 400 450-0.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2 2a 2b 2 naphthalene

Abs

orba

nce

(nor

mal

ized

)

Wavelength (nm)

250 300 350 400 450 500 550 600-0.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

2a 2b 2

Inte

nsity

(nor

mal

ized

)

Wavelength(nm)

2a 2b

O N

2

2a 2b

O N

2

chem f700830 s - wiley-vch · 40 (n-bu) 2n o o on(n-bu) 2 18 13c nmr (125mhz, cdcl3): £_13.55,...

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