42 Macromolecules, Vol. 43, No. 1, 2010
Nantalaksakul et al.
(2.99 mmol) of 2-phenyl-5-tributyl tin EDOT (10) in DMF
(50 mL). The mixture was deaerated several times and then handled
under argon. 0.07 g (0.10 mmol) of Pd(PPh3)2Cl2 was added and
the mixture was stirred at 80 °C for 2 h. After completion of the
reaction, water was added and the mixture was extracted using
CH2Cl2 (3 ꢀ 20 mL). Organic layers were collected and dried
over anhydrous MgSO4. The resulting residue was purified by
column choromatography using 10% ethyl acetate in dichlor-
omethane. The product was obtained as a yellow solid with 17%
yield. 1H NMR ((CD3)2CO, δ, ppm) 7.74 (br, 4H), 7.39 (t,
J = 7.7, 4H), 7.22 (br, 2H), 4.45 (s, 8H), 4.25 (d, J = 11.9, 2H),
nitrile by repeated scanning between -800 and þ800 mV at a
scan rate of 100 mV/s.
Chemical Cross-Linking of P1-P5 Using FeCl3 Followed by
Hydrazine. Polymers in dichloromethane were spun-coat on a
glass slide at a rate of 1000 rpm. The cross-linking of polymers
were preformed by dipping the film into an acetonitrile
solution containing 0.01 M FeCl3 for a few minutes. Then,
the film was washed with acetonitrile before it was dipped into
0.005 M hydrazine in acetonitrile for a few minutes. The film
was washed with acetonitrile and dried before recording the
absorption spectrum.
3.91 (d, J = 11.9, 2H), 3.78 (d, J = 6.0, 2H), 1.07 (s, 3H). 13
C
NMR ((CD3)2CO, δ, ppm): 144.1, 128.6, 126.2, 125.5, 76.3,
64.9, 63.0, 43.5, 15.9
Acknowledgment. We thank the National Science Founda-
tion’s Fueling the Future Center for Chemical Innovation for
partial support. The work here was also additionally supported
by the U.S. Army Research Office and the NSF-Center for
Hierarchical Manufacturing. We also thank Tejaswini Kale and
Bhooshan Popere for helping with some characterization experi-
ments.
Synthesis of 5-Norbornene-exo-2-triADOT Carboxylate (1).
A 0.10 g (0.21 mmol) sample of triADOT (6) and 0.06 g (0.43
mmol) of 5-exonorbornene-2-acetic acid (7) were dissolved
in dry THF, and the mixture was cooled down to 0 °C. Then
0.09 g (0.43 mmol) of dicyclohexyl carbodiimide (DCC) and
0.05 g (0.43 mmol) of 4-dimethyl aminopyridine (DMAP)
were added to the mixture portionwise. The mixture was
stirred at 0 °C for 2 h. After completion of the reaction, the
precipitated dicyclohexyl urea was filtered. Then, water was
added and the mixture was extracted using CH2Cl2 (3 ꢀ
20 mL). Organic layers were collected and dried over anhy-
drous MgSO4. The resulting residue was purified by column
choromatography using 30% ethyl acetate in hexanes. The
Supporting Information Available: Text giving synthetic and
other experimental details, drawings of structures of the com-
pounds, and figures showing TGA and DSC curves and absorp-
tion spectra of M1 and M2. This material is available free of
1
product was obtained as a yellow solid with 65% yield. H
NMR (CDCl3, δ, ppm) 6.29 (s, 2H), 4.37 (br, 4H), 4.31 (br,
1H), 4.27 (br, 4H), 4.21 (br, 1H), 3.87 (br, 2H), 3.10 (br, 1H),
2.96 (br, 1H), 2.33-2.28 (br, 1H), 1.96 (br, 1H), 1.43 (br, 3H),
1.07 (s, 3H). 13C NMR (CDCl3, δ, ppm): 176.2, 143.8, 141.0,
137.9, 137.2, 135.2, 113.1, 97.6, 66.3, 64.9, 64.2, 46.6, 43.1,
41.4, 33.9, 30.4, 16.6.
Synthesis of 5-Norbornene-exo-2-diphenyl triADOT Carboxy-
late (2). Similar to the procedure for 5-norbornene-exo-2-triA-
DOT (1), 0.10 g (0.16 mmol) of diphenyl triADOT (9), 0.04 g
(0.32 mmol) of 5-exonorbornene-2-acetic acid (7), 0.05 g (0.32
References and Notes
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mmol) of DCC, and 0.04
g (0.32 mmol) of DMAP
were employed. The crude product was purified by column
chromatography using 30% ethyl acetate in hexanes. The
product was obtained as a yellow solid with 69% yield. 1H
NMR (CDCl3, δ, ppm) 7.72 (br, 4H), 7.44 (br, 4H), 7.29 (br,
2H), 6.22 (br, 2H), 4.47 (d, J = 12.9, 8H), 4.36-4.22 (m, 4H),
3.96 (d, J = 9.6, 2H), 3.13 (br, 1H), 2.96 (br, 1H), 2.37 (br, 1H),
1.96-1.89 (m, 1H), 1.28 (br, 3H), 1.05 (s, 3H). 13C NMR
(CDCl3, δ, ppm): 176.5, 135.8, 128.6, 126.3, 124.8, 69.7, 66.6,
64.5,46.2, 43.1, 41.1, 30.4, 16.6
Syntheses of Polymers P1-P5 by Copolymerization of Mono-
mers 1 and 2. Dry THF was taken into a round-bottom flask and
was subjected to freeze-pump-thaw cycle 3 times before use.
The mixture of 1:0, 0:1, 3:1, 1:1, and 1:3 ratios of monomers 1
and 2 and third generation Grubbs catalyst were put under
vacuum into two separated round-bottom flasks for 30 min
before THF was added. Then, the solution of monomers in THF
was injected into a stirred solution of the catalyst. The mixture
was allowed to stir for 3 min at room temperature followed by
irreversible termination via the addition of 2 mL of ethyl vinyl
ether. The solution was then concentrated under vacuum. The
polymers were obtained by precipitating the mixture twice in
either methanol or ether. The precipitants were collected and
dried in vacuo to yield polymers as yellow solid. 1H NMR
(CDCl3, ppm) δ 7.81-7.61 (br, 4H), 7.26 (br, 6H), 6.30-6.05
(br, 2H), 5.50-4.88 (br, 4H), 4.27 (br, 24H), 3.92-3.54 (br, 4H),
3.19-2.79 (br, 4H), 2.79-2.28 (br, 2H), 2.28-1.67 (br, 8H),
1.33-0.69 (br, 6H).
Cross-Linked P1 and P2 by Oxidative Electropolymerization.
P1 and P2 in dichloromethane were spun-coat onto ITO-coated
glass, and electropolymerization was performed in 0.1 M tetra-
butyl ammonium hexafluorophosphate ((TBA)PF6) in aceto-