Macromolecules
ARTICLE
(CÀBr str.) 1512, 1460, 1063, 1014, 831, 756, 627 cmÀ1. HRMS: calcd
for C46H62N2O2Si2 = 730.4350; obsd = 730.4360; Δ = 1.4 ppm. Anal.
Calcd: C, 75.56; H, 8.55; N, 3.83. Found: C, 75.55; H, 8.45; N, 3.87.
2,3-Bis(4-(2-ethylhexyloxy)phenyl)-5,8-diethynylquinoxa-
line, 5a. A solution of tetra-n-butylammonium fluoride (1 M in THF,
6 mL, 6 mmol) was added to a solution of 4a (2.0 g, 2.7 mmol) in THF
(16 mL) under argon. The mixture was stirred at room temperature for
45 min and H2O (50 mL) was added. The mixture was extracted with
CH2Cl2 (2 Â 30 mL), the organic extracts were combined and the
solvent was removed under reduced pressure. Theresidue waspurifiedby
column chromatography (40:70 v/v CH2Cl2: hexanes) to afford the
diethynylÀquinoxaline monomer 5a as an orange viscous liquid (1.18 g,
73%). 1H NMR (300 MHz, CHCl3): δ 7.83 (s, 2H, quinoxaline CÀH),
7.62 (d, 3JHH = 8.7 Hz, 4H, Ph C2ÀH), 6.87 (d, 3JHH = 9 Hz, 4H, Ph
1.70À1.78 (m, 2H), 1.26À1.55 (m, 16H), 0.88À0.98 (m, 12H). 13C
NMR (75 MHz, CDCl3): δ 160.51 (Ph C4), 153.33 (quinoxaline C2 and
C3), 140.96 (quinoxaline C1 and C4), 133.20 (quinoxaline C6 and C7),
131.57 (Ph C2), 130.91 (Ph C1), 122.71 (quinoxaline C5 and C8),
114.36 (Ph C3), 85.00 (CtCÀH), 80.18 (CtCÀH), 70.56 (CÀO),
39.29, 30.48, 29.06, 23.81, 23.04, 14.09, 11.1. HRMS calcd for
C40H46N2O2 = 586.3559; obsd = 586.3565; Δ = 1.0 ppm. IR (ATIR):
3236 (CtCÀH str.) 2918 (Ar CÀH str.), 2148 (CtC str.), 1244, 1176
(CÀO str.), 1600 (CdN str.), 1478, 1379 (CÀC str.), 542 (CÀBr str.)
1512, 1460, 1063, 1014, 831, 756, 627 cmÀ1. Anal. Calcd: C, 81.87; H,
7.90; N, 4.77. Found: C, 82.01; H, 7.88; N, 4.84.
Poly(5,8-(2,3-bis(4(2-ethylhexyloxy)phenyl)quinoxaline
ethynylene), PQE(EH). A solution of dibromoquinoxaline 3a (1.0 g,
1.8 mmol) and diethynylquinoxaline 5a (3.7 g, 5.3 mmol) in THF
(25 mL) was degassed by two freezeÀpumpÀthaw cycles. Diisopropy-
lamine (5.0 mL, 35 mmol), CuI (55 mg, 0.29 mmol), and Pd(PPh3)4
(0.40 g, 0.35 mmol) were added, and the mixture was and heated at 45 °C
for 24 h. The mixture was poured into methanol (200 mL), and the
resulting precipitate was isolated by filteration. The solid was subjected to
sequential extraction with acetone, hexane, and chloroform in a Soxhlet
extractor. The solvent was removed from the chloroform fraction under
reduced pressure to afford the quinoxaline polymer PQE(EH) as a red
solid (0.842 g, 90%). 1H NMR (300 MHz, CHCl3): δ 7.78À7.67 (m,
4H), 7.40À7.37 (m, 8H), 6.80À6.7 (m, 8H), 3.94À3.68 (m, 8H),
1.26À1.55 (m, 36H), 0.95À0.84 (m, 24H). IR (ATIR): 2954 (Ar
CÀH str.), 1255, 1165 (CÀO str), 1371 (CÀC str.), 2848, 1599,
1509, 1254, 1003, 999, 787, 685, 498 cmÀ1. GPC (THF, refractive index
detector): Mn = 19 kg/mol, PDI = 2.1. Anal. Calcd: C, 75.73; H, 7.46, N,
4.71. Found: C, 75.19; H, 7.24; N, 4.05.
Georgia Tech Center for Organic Protonics and Electronics
(COPE) for scholarship support for K.B.W.
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3
C3ÀH), 3.87 (d, JHH = 6 Hz, 4H, ÀOCHH2À), 3.61 (s, 2H),
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S
Supporting Information. Experimental procedures for
b
analogues b and polymers used to compare spectroscopic data
(PQE(EH)-alt-PPE(C12), PPE(C12), and PQ((EH)), and
solid state spectra. This material is available free of charge via
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: david.collard@chemistry.gatech.edu.
’ ACKNOWLEDGMENT
E.M.H. was supported as a visiting researcher from the
University of the South by an NSF Research Experiences for
Undergraduates program (NSF 0851780). We also thank the
ACS Organic Division (Nelson Leonard Fellowship) and the
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D.; Blom, P.W. M.; Hummelen, J. C. Chem. Mater. 2006, 18, 3068–3073.
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dx.doi.org/10.1021/ma201347z |Macromolecules 2011, 44, 9118–9124