chem f700830 s - Wiley-VCH · 40 (n-Bu) 2N O O ON(n-Bu) 2 18 13C NMR (125MHz, CDCl3): £_13.55,...
Transcript of 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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Supporting Information
© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2008
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Syntheses of Ladder-Type Oligonaphthalene Derivatives and Their
Photophysical and Electrochemical Properties
Jun-Chun Chen, Tse-Shi Lee, Chih-Hsiu Lin*
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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
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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
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4
O N
O 14O
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5
O N
O OMe 14
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6
OMe
N(n-Bu)2O
1
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7
OMe
N(n-Bu)2O
1
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8
O
N(n-Bu)2
2
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9
O
N(n-Bu)2
2
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10
N(n-Bu)2O
OMe
3
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11
N(n-Bu)2O
OMe
3
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12
4
O N(n-Bu)2
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13
4
O N(n-Bu)2
-
CF3
OMe
5
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15
CF3
OMe
5
-
CF3
6
16
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17
CF3
6
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18
O
O O
O
N(n-Bu)2
(n-Bu)2N
7
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19
O
O O
O
N(n-Bu)2
(n-Bu)2N
7
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O N(n-Bu)2
O(n-Bu)2N
OH
OH
8'
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O N(n-Bu)2
O(n-Bu)2N
OH
OH
8'
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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).
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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.
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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).
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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.
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O
O
O
O
N(n-Bu)2
(n-Bu)2N
10
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O
O
O
O
N(n-Bu)2
(n-Bu)2N
10
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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).
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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.
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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).
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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.
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O N(n-Bu)2
OMe Br
13
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O N(n-Bu)2
OMe Br
13
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O
O
(n-Bu)2N
15
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O
O
(n-Bu)2N
15
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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).
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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.
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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).
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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.
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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).
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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.
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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).
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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.
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8R OMe
R OMe
16R OMe
R OMe
R OMe
17R OMe
R OMe RMeO
RMeO
R =o
N(n-Bu)2
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46
8R OMe
R OMe
16R OMe
R OMe
R OMe
17R OMe
R OMe RMeO
RMeO
R =o
N(n-Bu)2
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47
8R OMe
R OMe
R =o
N(n-Bu)2
16R OMe
R OMe
R OMe
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48
R
R 9
R
R 18 R
R
R19
R
R
R =o
N(n-Bu)2
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49
R =o
N(n-Bu)2
R
R 9
R
R 18 R
R
R19
R
R
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50
R
R 9
R =o
N(n-Bu)2
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51
O
F3C
23
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52
O
F3C
23
-
O
O
CF3
F3C
20
53
-
O
O
CF3
F3C
20
54
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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)
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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
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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
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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
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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)
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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
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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)
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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
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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)
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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
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65
OH
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66
OH
-
67
-
68
-
69
OH
-
70
OH
-
71
-
72
-
73
OH
-
74
OH
-
75
-
76
-
77
OH
-
78
OH
-
79
16
-
80
-
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
)
Potential ( V vs Ag/AgNO3)
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
Potential ( V vs Ag/AgNO3)
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
)
Potential ( V vs Ag/AgNO3)
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