6-((1E)-2-(5-((1E)-2-(2, 5-Bis(2-ethylhexyloxy)-4-((1E)-
2-(5-((E)-2-(3,3-dibutyl-3,4-dihydro-2H-thieno[3,4-b][1,4]
dioxepin-6-yl)vinyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)vinyl)phenyl)vinyl)-2,3-
dihydrothieno[3,4-b][1,4]dioxin-7-yl)vinyl)-3,3-dibutyl-3,4-dihydro-2H-
thieno[3,4-b][1,4] dioxepine, E,E,E,E-45: Yield: 80%. 1H NMR (300 MHz,
CDCl3, δppm): 7.19 (d, 2H), 7.14 (d, 2H), 6.97 (d, 2H), 6.87 (d, 4H), 6.25
(s, 2H), 4.27 (s, 8H), 3.91 (d, 8H), 3.84 (d, 4H), 1.54 (t, 2H), 1.39 (m,
N-(4-((1E)-2-(6-(4-((1E)-2-(6-(4-(Diphenylamino)styryl)-3,3-dibutyl-
3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-8-yl)vinyl)-2,5-bis(octan-3-yloxy)
styryl)-3,3-dibutyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-8-yl)vinyl)
phenyl)-N-phenylbenzenamine, E,E,E,E-51: Yield: 88%. 1H NMR (300
MHz, CDCl3, δppm): 77.62 (d, 4H), 7.60 (m, 16H), 7.24 (m, 16H), 6.95
(d, 4H), 4.26 (s, 8H), 4.20 (t, 4H), 3.92 (s, 4H), 1.81 (m, 2H), 1.21 (m,
40H), 1.15 (s, 6H), 0.72 (m, 18H); 13C NMR (75 MHz, CDCl3,
δppm):
40H), 0.80 (m, 24H); 13C NMR (75 MHz, CDCl3,
δ
ppm): 141.51, 139.18,
178.01, 149.98, 148.21, 145.62, 139.81, 136.08, 133.91, 132.84, 131.01,
128.97, 127.62, 126.54, 126.21, 125.82, 125.03, 124.94, 124.08, 118.2,
113.8, 97.2, 79.5, 77.79,.31.49, 31.40, 30.01, 28.65, 24.7, 23.6, 22.49,
21.70, 14.03; HRMS (ESI) m/z: [M+H]+ calcd for C96H116N2O6S2,
1457.8274; found, 1457.8189.
139.14, 126.32, 121.82, 121.16, 117.74, 116.52, 116.30, 115.61, 115.16,
109.71, 101.80, 71.58, 64.80, 43.58, 43.55, 39.77, 31.46, 31,42, 30.80,
29.62, 29.33, 24.12, 23.48, 23.08, 23.04, 22.58, 14.03, 13.93; HRMS (ESI)
m/z: [M+H]+ calcd for C72H98O10S4, 1251.6042; found, 1251.4038.
(1E,2E)-1-((2Z)-3-((3E)-4-(2,5-Bis(2-ethylhexyloxy)-4-((1E)-2-(5-(4-
(dibutylamino)styryl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)vinyl)phenyl)
but-3-en-2-ylidene)-1,4-dioxan-2-ylidene)-3-(4-(dibutylamino)phenyl)prop-
2-ene-1-thiol, E,E,E,E-46: Yield: 85%. 1H NMR (300 MHz, CDCl3, δppm):
7.23 (d, 4H), 7.18 (d, 4H), 7.07 (d, 2H), 6.95 (d, 4H), 6.69 (d, 2H), 6.58
(d, 4H), 4.27 (s, 8H), 3.92 (d, 4H), 3.26 (t, 8H), 1.81 (m, 2H), 1.57-1.38
6-(4-((1E)-2-(3,3-Dibutyl-6-((E)-2-(5-hexylthiophen-2-yl)vinyl)-3,4-
dihydro-2H-thieno[3,4-b]1,4]dioxepin-8-yl)vinyl)-2,5-bis(octan-3-yloxy)styryl)-
3,3-dibutyl-8-((E)-2-(5-hexyl thiophen-2-yl)vinyl)-3,4-dihydro-2H-thieno[3,4-b]
1
[1,4]dioxepine, E,E,E,E-52: Yield: 87%. H NMR (300 MHz, CDCl3, δppm):
7.27 (d, 4H), 6.99 (d, 2H), 6.83 (d, 4H), 6.77 (d, 2H), 6.60 (d, 2H), 4.3 (s,
8H), 3.92 (d, 4H), 2.71 (t, 4H), 1.81 (m, 2H), 1.54 (t, 4H), 1.29 (m, 28H),
(m, 32H), 0.94 (t, 24H); 13C NMR (75 MHz, CDCl3,
δ
ppm): 150.94, 147.46,
1.19 (m, 24H), 0.80 (m, 30H); 13C NMR (75 MHz, CDCl3,
δppm): 151.01,
139.22, 138.11, 127.39, 126.66, 126.32, 124.35, 120.47, 117.65, 116.71,
115.24, 112.91, 111.52, 109.60, 71.62, 64.88, 64.64, 50.68, 39.74, 30.81,
29.42, 29.22, 24.10, 23.07, 20.26, 14.14, 14.05, 13.93, 11.33; HRMS (ESI)
m/z: [M+H]+ calcd for C71H100N2O6S2, 1125.6709; found, 1125.7060.
4-((1E)-2-(5-(2,5-Bis(2-ethylhexyloxy)-4-((1E)-2-(5-(4-(diphenylamino)
styryl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)vinyl)styryl)-2,3-dihydrothieno-
[3,4-b][1,4]dioxin-7-yl)vinyl)-N,N-diphenyl benzenamine, E,E,E,E-47: Yield:
80%. 1H NMR (300 MHz, CDCl3, δppm): 8.18(d, 4H), 7.62(d, 2H), 7.60
(m, 8H), 7.24(d, 8H), 7.04(d, 2H), 4.26(s, 8H), 4.20(t, 4H), 3.944(d,
4H), 1.83 (m, 6H), 1.61 (q, 4H), 1.47(m, 28H), 1.01(m, 12H), 0.87(t,
145.02, 140.73, 139.19 139.05, 126.35, 125.48, 124.60, 121.14, 119.90,
117.62, 116.51, 116.38, 115.24, 109.60, 71.55, 64.80 39.77, 31.54, 31,42,
30.37, 30.11, 29.66, 29.62, 29.33, 29.26, 28.72, 24.14, 23.11, 22.65, 22.54,
14.17, 14.05, 11.36; HRMS (ESI) m/z: [M+H]+ calcd for C80H118O6S4,
1303.7811; found, 1303.7853.
6-[(E)-2-[5-[(E)-2-[7-[(E)-2-[4-[(E)-2-[5-[(E)-2-[7-[(E)-2-(3,3-Dimethyl-2,4-
dihydrothieno[3,4-b][1,4]dioxepin-6-yl)vinyl]-2,3-dihydrothieno[3,4-b][1,4]
dioxin-5-yl]vinyl]-2,3-di
hydrothieno[3,4-b][1,4]dioxin-7-yl]vinyl]-2,5-bis(2-
ethylhexoxy)phenyl]vinyl]-2,3-dihydroth ieno[3,4-b][1,4]dioxin-5-yl]vinyl]-2,3-
dihydrothieno[3,4-b][1,4]dioxin-7-yl]vinyl]-3,3-dimethyl-2,4-
dihydrothieno[3,4-b][1,4]dioxepine, E,E,E,E,E,E-53: Yield: 86%. 1H NMR
(300 MHz, CDCl3, δppm): 7.19 (d, 2H), 7.04 (d, 4H), 6.97 (d, 4H), 6.87
(d, 4H), 6.25 (s, 2H), 4.27 (s, 8H), 3.91 (d, 16H), 3.84 (d, 4H), 1.54 (t,
6H); 13C NMR (75 MHz, CDCl3,
δppm): 151.01, 145.07, 140.73, 139.19,
139.16, 128.52, 126.35, 125.48, 124.60, 121.14, 116.51, 115.24, 109.60,
71.55, 64.80, 39.77, 31.54, 31.42, 30.85, 30.37, 29.66, 29.26, 28.72, 24.14,
23.11, 22.54, 14.17, 14.05, 11.36; HRMS (ESI) m/z: [M+H]+ calcd for
C78H80N2O6S2, 1205.5457; found, 1205.3567.
2-((1E)-2-(5-((1E)-2-(2,5-Bis(2-ethylhexyloxy)-4-((1E)-2-(5-((E)-2-(9-
hexyl-9H-carbozol-2-yl)vinyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)vinyl)
phenyl)vinyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)vinyl)-9-hexyl-9H-
carbazole, E,E,E,E-48: Yield: 85%. 1H NMR (300 MHz, CDCl3, δppm):
8.18 (d, 4H), 7.62 (d, 2H), 7.60 (m, 8H), 7.24 (d, 8H), 7.04 (d, 2H),
4.26 (s, 8H), 4.20 (t, 4H), 3.944 (d, 4H), 1.83 (m, 6H), 1.61 (q, 4H),
1.47 (m, 28H), 1.01 (m, 12H), 0.87 (t, 6H); 13C NMR (75 MHz, CDCl3,
2H), 1.39 (m, 40H), 0.80 (m, 24H); 13C NMR (75 MHz, CDCl3,
δppm):
141.51, 139.18, 139.14, 126.32, 121.82, 121.16, 117.74, 116.52, 116.30,
115.61, 115.16, 109.71, 101.80, 71.58, 64.80, 43.58, 43.55, 39.77, 31.46,
31,42, 30.80, 29.62, 29.33, 24.12, 23.48, 23.08, 23.04, 22.58, 14.03, 13.93;
HRMS (ESI) m/z: [M+H]+ calcd for C88H110O14S6, 1584.6219; found,
1584.6238.
5-[(E)-2-[7-[(E)-2-[2,5-Bis(2-ethylhexoxy)-4-[(E)-2-[5-[(E)-2-
[7-[(E)-2-(5-methyl-2-thienyl)vinyl]-2,3-dihydrothieno[3,4-b][1,4]
dioxin-5-yl]vinyl]-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl]vinyl]phenyl]vinyl]-
2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl]vinyl]-7-[(E)-2-(5-methyl-2-thienyl)
vinyl]-2,3-dihydrothieno[3,4-b][1,4]dioxine, E,E,E,E,E,E-54: Yield: 90%. 1H
NMR (300 MHz, CDCl3, δppm): 7.19 (d, 4H), 6.89 (d, 2H), 6.80 (d, 4H),
6.77 (d, 4H), 6.60 (d, 4H), 4.27 (s, 16H), 3.90 (d, 4H), 2.71 (t, 4H), 1.54
δppm): 151.01, 145.07, 140.73, 139.19, 139.16, 128.52, 126.35, 125.48,
124.60, 121.14, 116.51, 115.24, 109.60, 71.55, 64.80, 39.77, 31.54, 31.42,
30.85, 30.37, 29.66, 29.26, 28.72, 24.14, 23.11, 22.54, 14.17, 14.05, 11.36;
HRMS (ESI) m/z: [M+H]+ calcd for C78H92N2O6S2, 1217.6396; found,
1217.5446.
(t, 4H), 1.29 (m, 28H), 0.80 (m, 18H); 13C NMR (75 MHz, CDCl3,
δppm):
(1E,2E)-1-((2Z)-3-((3E)-4-(2,5-Bis(2-ethylhexyloxy)-4-((1E)-2-(5-(3,4,5-
trimethoxystyryl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)vinyl)phenyl)
but-3-en-2-ylidene)-1,4-dioxan-2-ylidene)-3-(3,4,5-trimethoxyphenyl)prop-
2-ene-1-thiol, E,E,E,E-49: Yield: 83%. 1H NMR (300 MHz, CDCl3, δppm):
7.23 (s, 2H), 6.97 (d, 4H), 6.78 (d, 4H), 6.78 (d, 4H), 6.19 (s, 2H), 4.24
(s, 8H). 3.89 (m, 22H), 1.82 (m, 2H), 1.23 (m, 16H), 0.85 (m, 12H);
151.01, 145.02, 140.73, 139.19 139.05, 126.35, 125.48, 124.60, 121.14,
119.90, 117.62, 116.51, 116.38, 115.24, 109.60, 71.55, 64.80 39.77, 31.54,
31,42, 30.37, 30.11, 29.66, 29.62, 29.33, 29.26, 28.72, 24.14, 23.11,
22.65, 22.54, 14.17, 14.05, 11.36; HRMS (ESI) m/z: [M+H]+ calcd for
C
78H94O10S6, 1383.5171; found, 1383.9637.
13C NMR (75 MHz, CDCl3,
δppm): 151.24, 148.76, 138.28, 136.11, 128.37,
126.66, 126.32, 124.55, 120.47, 117.65, 116.71, 115.24, 112.91, 111.52,
109.60, 71.62, 64.88, 64.64, 50.68, 56.06, 39.74, 30.81, 29.42, 29.22,
24.10, 23.07, 20.26, 14.14, 13.93, 11.33; HRMS (ESI) m/z: [M + H]+ calcd
for C61H78O12S2, 1067.4925; found, 1067.5809 (M+H+).
Acknowledgements
The authors thank the European Community Marie Curie Actions, Marie
Curie Research Training Network (BIMORE, Project No.: 35859, grant
agreement No: 2008206) and the Technion Funds for Security Research.
This article was amended on April 10, 2012 to correct an error in the
spelling of author K. N. Shivananda’s name that was present in the
version originally published online.
5-(2,5-Bis(2-ethylhexyloxy)-4-((1E)-2-(5-((E)-2-(5-hexylthiophen-2-yl)
vinyl)-2,3-dihy
drothieno[3,4-b][1,4]dioxin-7-yl)vinyl)styryl)-7-((E)-2-(5-
hexylthiophen-2-yl)vinyl)-2,3-dihy drothieno[3,4-][1,4]dioxine, E,E,E,E-50:
Yield: 91%. 1H NMR (300 MHz, CDCl3, δppm): 7.17 (d, 4H), 6.97 (d, 2H),
6.83 (d, 4H), 6.77 (d, 2H), 6.60 (d, 2H), 4.27 (s, 8H), 3.90 (d, 4H), 2.71
(t, 4H), 1.54 (t, 4H), 1.29 (m, 28H), 0.80 (m, 18H); 13C NMR (75 MHz,
Received: August 13, 2011
Published online: January 31, 2012
CDCl3,
δppm): 151.01, 145.02, 140.73, 139.19 139.05, 126.35, 125.48,
124.60, 121.14, 119.90, 117.62, 116.51, 116.38, 115.24, 109.60, 71.55,
64.80 39.77, 31.54, 31,42, 30.37, 30.11, 29.66, 29.62, 29.33, 29.26, 28.72,
24.14, 23.11, 22.65, 22.54, 14.17, 14.05, 11.36; HRMS (ESI) m/z: [M+H]+
calcd for C62H82O6S4,1051.4994; found, 1051.5013.
[1] a) K. Müllen, U. Scherf, Organic Light Emitting Devices, Wiley-VCH,
Weinheim 2006; b) T. Yokozawa, A. Yokoyama, Chem. Rev. 2009,
109, 5595.
©
1500 wileyonlinelibrary.com
2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Funct. Mater. 2012, 22, 1489–1501