Bis-enediynes as Tunable Fluorophores
A R T I C L E S
1,4-Bis[4-phenyl-2-(phenylethynyl)but-1-en-3-ynyl]-2-ni-
trobenzene (26). Prepared according to procedure A. Column
chromatography (SiO2; hexane/EtOAc, 30:1), yield: 38%. M.p.
136-137 °C; IR (film): 3061, 2196, 1645, 1601, 1528, 1490,
126.8, 125.6, 122.8, 122.1, 110.9, 94.5, 88.8, 87.9, 86.3; MS
(FAB) m/z 630.0 [M+]; Anal. Calcd. for C50H30: C, 95.21; H,
4.79. Found: C, 94.85; H, 4.71.
1,4-Bis[4-phenyl-2-(phenylethynyl)but-1-en-3-ynyl]-2,5-
dimethoxybenzene (31). Prepared according to procedure A.
Column chromatography (SiO2; hexane/EtOAc, 30:1), yield:
18%. M.p. 214-216 °C; IR (film): 3041, 2945, 2831, 2190,
1636, 1597, 1487, 1410, 1313, 1278, 1210, 1041, 896, 854, 758
cm-1; 1H NMR (300 MHz, CDCl3): δ 8.20 (s, 2H, ArH), 7.59
(s, 2H, CdCH), 7.56-7.52 (m, 8H, ArH), 7.37-7.33 (m, 12H,
ArH), 3.75 (s, 6H, OCH3); 13C NMR (75 MHz, CDCl3): δ
151.0, 136.6, 131.7, 131.5, 128.8, 128.5, 128.4, 128.3, 126.4,
123.0, 122.7, 110.2, 102.9, 95.3, 89.8, 87.3, 56.0; MS (FAB)
m/z 590.2 [M+]; Anal. Calcd. for C44H30O2: C, 89.46; H, 5.12.
Found: C, 89.15; H, 5.48.
2,5-Bis[4-phenyl-2-(phenylethynyl)but-1-en-3-ynyl]thio-
phene (32). Prepared according to procedure A. Column
chromatography (SiO2; hexane), yield: 78%. M.p. 134-136 °C;
IR (film): 3060, 2193, 1655, 1559, 1490, 1252, 1024, 913, 876,
798, 753 cm-1; 1H NMR (300 MHz, CDCl3): δ 7.62-7.56 (m,
8H, ArH), 7.48 (s, 2H, ArH), 7.43-7.39 (m, 6H, ArH), 7.37
(s, 2H, CdCH), 7.28-7.26 (m, 6H, ArH); 13C NMR (75 MHz,
CDCl3): δ 142.0, 135.6, 131.6, 131.5, 130.6, 128.6, 128.4,
128.3, 128.2, 122.8, 122.4, 101.7, 98.1, 90.0, 89.2, 87.5; MS
(FAB) m/z 536.1 [M+]; Anal. Calcd. for C40H24S1: C, 89.52;
H, 4.51. Found: C, 89.23; H, 4.64.
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1344, 1098, 908, 876, 824, 753 cm-1; H NMR (300 MHz,
CDCl3): δ 8.96 (s, 1H, ArNO2H), 8.37 (d, 1H, J ) 8.3 Hz,
ArNO2H), 8.00 (d, 1H, J ) 8.4 Hz, ArNO2H), 7.64-7.55
(m, 8H, ArH), 7.45-7.30 (m, 13H, ArH and CdCH), 7.16 (s,
1H, CdCH); 13C NMR (75 MHz, CDCl3): δ 147.9, 138.9,
136.9, 132.5, 131.9, 131.8, 131.7, 130.7, 129.3, 129.0, 128.8,
128.5, 128.4, 128.1, 124.1, 122.5, 122.2, 122.0, 108.1, 106.8;
MS (FAB) m/z 575.1 [M+]; Anal. Calcd. for C42H25N1O2: C,
87.63; H, 4.38; N, 2.43. Found: C, 87.55; H, 4.29; N, 2.27.
2,6-Bis[4-phenyl-2-(phenylethynyl)but-1-en-3-ynyl]naph-
thalene (27). Prepared according to procedure A. Column
chromatography (SiO2; hexane/EtOAc, 25:1), yield: 57%. M.p.
166-168 °C; IR (film): 3049, 2198, 1597, 1538, 1489, 1458,
1216, 1025, 907, 811, 755 cm-1; 1H NMR (300 MHz, CDCl3):
δ 8.39 (s, 2H, ArnaphH), 8.13 (dd, 2H, J ) 8.6, 1.0 Hz, ArnaphH),
7.84 (d, 2H, J ) 8.6 Hz, ArnaphH), 7.63-7.55 (m, 8H, ArH),
7.42-7.35 (m, 12H, ArH), 7.32 (s, 2H, CdCH); 13C NMR (75
MHz, CDCl3): δ 142.8, 134.3, 133.2, 131.7, 131.6, 128.8, 128.7,
128.5, 128.3, 128.0, 127.8, 126.7, 126.5, 122.9, 122.8, 103.8,
95.2, 89.4, 89.0, 87.3; MS (FAB) m/z 580.2 [M+]; Anal. Calcd.
for C46H28: C, 95.14; H, 4.86. Found: C, 94.88; H, 4.97.
2,7-Bis[4-phenyl-2-(phenylethynyl)but-1-en-3-ynyl]-9,9-
dipropylfluorene (28). Prepared according to procedure A.
Column chromatography (SiO2; hexane/CH2Cl2, 10:1), yield:
87%. M.p. 96-98 °C; IR (film): 3042, 2957, 2869, 2206, 1600,
1,4-Bis[4-phenyl-2-(phenylethynyl)-1-methylbut-1-en-3-
ynyl]benzene (33). Prepared according to procedure A. Column
chromatography (SiO2; hexane/EtOAc, 30:1), yield: 56%. M.p.
79-80 °C; IR (film): 3058, 2926, 2205, 1597, 1490, 1444,
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1490, 1456, 1216, 1171, 1098, 1025, 906, 818, 755 cm-1; H
1
NMR (300 MHz, CDCl3): δ 8.11 (s, 2H, ArH), 7.95 (d, 2H, J
) 7.9 Hz, ArH), 7.77 (d, 2H, J ) 8.0 Hz, ArH), 7.67-7.60 (m,
8H, ArH), 7.45-7.39 (m, 12H, ArH), 7.33 (s, 2H, CdCH), 1.97
1271, 1066, 1020, 916, 837, 755 cm-1; H NMR (300 MHz,
CDCl3): δ 7.74 (s, 4H, ArH), 7.58-7.55 (m, 4H, ArH), 7.39-
7.29 (m, 10H, ArH), 7.28-7.19 (m, 6H, ArH), 2.55 (s, 6H,
CH3); 13C NMR (75 MHz, CDCl3): δ 131.5, 131.3, 128.6,
128.3, 128.1, 127.8, 127.6, 127.3, 127.2, 123.2, 123.1, 102.4,
93.8, 90.8, 87.7, 87.5, 22.4; MS (FAB) m/z 558.1 [M+]; Anal.
Calcd. for C44H30: C, 94.59; H, 5.41. Found: C, 94.51; H, 5.73.
9,10-Bis[3-phenyl-1-(phenylethynyl)prop-2-ynylidene]-9,-
10-dihydroanthracene (34). Prepared according to procedure
A. Column chromatography (SiO2; hexane/EtOAc, 20:1),
yield: 51%. M.p. 121-122 °C; IR (film): 3058, 2188, 1595,
(t, 4H, J ) 3.9 Hz, CCH2), 0.75-0.66 (m, 10H, CH2CH3); 13
C
NMR (75 MHz, CDCl3): δ 151.6, 143.7 (d), 141.6, 135.1,
131.8, 131.5, 128.8, 128.3, 128.0, 123.3, 123.0, 123.0, 122.9,
102.4, 95.0, 89.6, 88.5, 87.3, 42.6, 29.7, 17.2, 14.3; MS (FAB)
m/z 702.2 [M+]; Anal. Calcd. for C55H42: C, 93.98; H, 6.02.
Found: C, 93.61; H, 6.18.
1,4-Bis[4-phenyl-2-(phenylethynyl)but-1-en-3-ynyl]ben-
zene (29). Prepared according to procedure A. Column chro-
matography (SiO2; hexane), yield: 60%. M.p. 182-185 °C; IR
(film): 3062, 2195, 1599, 1489, 1442, 1287, 1069, 1024, 895,
1
1488, 1444, 1408, 1261, 1093, 1022, 866, 801, 755 cm-1; H
NMR (300 MHz, CDCl3): δ 8.53 (q, 4H, J ) 3.0 Hz, ArAQH),
7.57-7.55 (m, 8H, ArH), 7.47 (q, 4H, J ) 3.0 Hz, ArAQH),
7.39-7.37 (m, 12H, ArH); 13C NMR (75 MHz, CDCl3): δ
145.7, 134.6, 131.6, 128.5, 128.3, 127.4, 127.2, 123.1, 100.8,
93.7, 89.2; MS (FAB) m/z 604.1 [M+]; Anal. Calcd. for
C48H28: C, 95.33; H, 4.67. Found: C, 95.09; H, 4.74.
(4-Phenyl-2-phenylethynylbut-1-en-3-ynyl)benzene (35).
Prepared according to procedure A. Column chromatography
(SiO2; hexane/EtOAc, 15:1), yield: 86%. M.p. 118-119 °C;
IR (film): 3059, 2198, 1597, 1490, 1446, 1378, 1265, 1070,
1025, 918, 755 cm-1; 1H NMR (300 MHz, CDCl3): δ 7.99 (d,
2H, J ) 6.9 Hz, ArH), 7.61-7.57 (m, 4H, ArH), 7.47-7.35
(m, 9H, ArH), 7.22 (s, 1H, CdCH); 13C NMR (75 MHz,
CDCl3): δ 143.1, 135.6, 131.6, 129.1, 129.0, 128.7, 128.4,
128.3, 128.0, 126.5, 122.8, 122.7, 103.2, 94.6, 89.1, 88.3, 86.9;
MS (FAB) m/z 304.0 [M+].
1
817, 753 cm-1; H NMR (300 MHz, CDCl3): δ 7.98 (s, 4H,
ArH), 7.55-7.52 (m, 8H, ArH), 7.38 (m, 12H, ArH), 7.15 (s,
2H, CdCH); 13C NMR (75 MHz, CDCl3): δ 142.2, 136.5,
131.7, 131.6, 129.0, 128.8, 128.5, 128.3, 122.9, 122.8, 104.0,
95.4, 89.4, 89.1, 87.2; MS (FAB) m/z 530.2 [M+]; Anal. Calcd.
for C42H26‚0.5H2O: C, 93.48; H, 5.04. Found: C, 93.44; H,
4.87.
9,10-Bis[4-phenyl-2-(phenylethynyl)but-1-en-3-ynyl]an-
thracene (30). Prepared according to procedure A. Column
chromatography (SiO2; hexane/CH2Cl2, 6:1), yield: 61%. M.p.
177-179 °C; IR (film): 3063, 2202, 1650, 1490, 1444, 1372,
1
1270, 1101, 1025, 912, 802, 753 cm-1; H NMR (300 MHz,
CDCl3): δ 8.35 (2 d, 4H, J ) 6.8 Hz, ArH), 8.16 (s, 2H, Cd
CH), 7.67 (2 d, 4H, J ) 7.7 Hz, ArH), 7.56 (2 d, 4H, J ) 6.8
Hz, ArH), 7.42-7.38 (m, 8H, ArH), 7.08-6.92 (m, 4H, ArH),
6.66 (d, 4H, J ) 7.3 Hz, ArH); 13C NMR (75 MHz, CDCl3):
δ 142.0, 131.9, 131.3, 131.1, 129.0, 128.7, 128.4, 128.3, 127.8,
Absorption and Fluorescence Measurements. Absorption
and fluorescence spectra were recorded using 10-5-10-6
M
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J. AM. CHEM. SOC. VOL. 125, NO. 37, 2003 11247