Synthesis and Optical Properties of Phthalonitrile Oligomers
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NC RO
N
RO
-
N
-
+
N
N
[
N
]n
NC
CN
pi-Acceptor NC
Electron Transfer
Donor-Acceptor Complex
+
pi-Donor Complex
N
RO
CN
CN
(
)
-.
-
N
N
N
N
-
Anionic Propagation Route A: Electron transfer via a complex resulting in anionic propagation RO
[
N
N]
N
N M(OR) 2
n
RO
[
N
N]
N n
N
-
+ M(OR)2
n _< 3 NC
CN
RO
[
N
N]
N
N
-
+ M(OR)2
n+1
Complex
Route B: Chain growth via a Lewis acid-base interaction.
Figure 1 Sn(OCH3)2 + 2 NaBr Na2[Sn(OCH3)4] 2 Sn(OCH3)2 + 2 NaBr
SnBr2 + 2 NaOCH3 Sn(OCH3)2 + 2 NaOCH3 Na2[Sn(OCH3)4] + SnBr2 Figure 2 EXPERIMENT
Oligo-isoindoline Sodium (0.51g, 22 mmol) was dissolved in 30 ml of absolute methanol, 2-methoxy -ethanol or N,N-dimethylethanolamine, and followed by stannous chloride (1.9 g, 10 mmol). After 15 minutes , a white suspension was formed. Phthalonitrile (0.64 g, 5 mmol) was added and refluxed for two days. After solution cooling, the precipitate was collected by filter and washed with methanol. The solid was transferred into 150 ml of 0.5 M NaOH solution. The insoluble tin(II) phthalocyanine (0.116 g, 14.7%) was collected and dried in the vacuum oven. The alcohol filtrate was concentrated by vacuum distillation. The remaining solid was put into 150 ml of 0.5 M NaOH solution under ultrasonication to help dissolve tin salt. The insoluble solid was collected and dried in the vacuum oven. The solid was transferred into thimble for soxhlet extraction with toluene as eluent. The solid in the thimble was dried in vacuum oven to give oligomers (0.207 g, 32.3%).1H-NMR (DMSOd6, ppm) 0.85(s ); 1.22(s ); 7.0-9.0 (br). 13C-NMR (DMSO-d6, ppm) 25.53; 29.88; 120.83; 122.73; 123.03; 123.55; 129.67; 130.39; 130.91; 132.58; 133.04; 133.96; 134.31; 134.90;
135.11; 171.27. IR (KBr, cm-1) 712; 795; 841; 1082; 1183; 1330; 1383; 1485; 1659; 3369. UV-vis (DMF); λmax 425.nm Oligo-4-methoxyisoindoline 4-Methoxyphthalonitrile was synthesized by Siegl procedure [17]. Sodium (0.51g, 22 mmol) was dissolved in 30 ml of absolute methanol, 2-methoxy -ethanol or N,N-dimethylethanolamine, and followed by stannous chloride (1.9 g, 10 mmol). After 15 minutes , a white suspension was formed. 4Methoxyphthalonitrile (0.79 g, 5 mmol) was added and refluxed for two days. After solution cooling, the precipitate was collected by filter and washed with methanol. The solid was transferred into 150 ml of 0.5 M NaOH solution. The insoluble tin(II) phthalocyanine did not find. The alcohol filtrate was concentrated by vacuum dis tillation. The remaining solid was put into 150 ml of 0.5 M NaOH solution under ultrasonication to help dissolve tin salt. The insoluble solid was collected and dried in the vacuum oven. The solid was transferred into thimble for soxhlet extraction with toluene as eluent. The solid in the thimble was dried in vacuum oven to give oligomers (0.28 g, 35.4%).1H-NMR (DMSOd6, ppm) 0.84(s ), 1.25(s ), 3.89(s ), 7.0-9.0(br.,m). 13C-NMR (DMSO-d6, ppm) 56.60, 56.81, 57.08,107.77,108.73, 120.67, 124.20, 125.54, 163.68. IR (KBr, cm-1) 736, 829, 1022, 1065, 1093,
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