42
J.-T. Miao et al. / Dyes and Pigments 105 (2014) 41e46
directly. Chromatography was performed with silica gel (200e300
mesh).
CH2), 1.23 (s, 10H, 5 ꢀ CH2), 0.86 (t, J ¼ 6.5 Hz, 3H, CH3). 13C NMR
(75 MHz, CDCl3) d 169.80, 153.87, 147.38, 140.66, 137.77, 135.40,
131.09, 130.32, 129.16, 128.31, 126.51, 125.79, 118.71, 115.18, 103.54,
57.38, 31.80, 30.00, 29.30, 26.51, 23.60, 22.63, 14.11. MS (ESIþ) m/z:
calcd for C29H37N2Oþ: 429.2906, found: 429.2892 [M-Iꢁ]þ.
2.2. Instruments
Melting points were determined on an Xe4 microscope electron
thermal apparatus (Taike, China) and the values are uncorrected.
NMR spectra were recorded on a Varian-300 or 400 MHz spec-
trometer. Mass spectra were recorded on Finnigan MAT95 mass
spectrometer. UVevis absorption spectra were recorded on a Shi-
madzu Ue3900 spectrometer. Atomic force microscope (AFM)
images were tested with a Bruker dimension icon system. The
thickness of the films was obtained by a Hitachi Se4700 scanning
electron microscope (SEM).
2.3.4. Synthesis of 1-ethyl-4-(3-(1-ethylquinolin-4(1H)-ylidene)
prop-1-en-1-yl)quinolin-1-ium iodide (3a)
To a mixture of 2a (201.0 mg, 0.5 mmol) and 1a (149.5 mg,
0.5 mmol) in ethanol (5 mL), Et3N (0.15 mL) was added in portions,
and then the mixture was refluxed for 1 h. The reactant was cooled
to room temperature; the product was separated by filtration and
recrystallized from methanol to give dark green powder. Yield:
42.5%, mp 248.3e250.2 ꢂC; 1H NMR (400 MHz, DMSO)
d 8.70 (t,
The third-order NLO properties were measured by the Z-scan
technique as reported method [16,17], laser pulses at wavelength of
532 nm with pulse width of 4 ns (fwhm) were generated from a
frequencyedoubled and Q-switched Nd:YAG laser and an Nd:YAG
532 nm laser (EKSPLA) with a pulse width of 21 ps (fwhm) and
repetition rate of 10 Hz was used for picosecond measurements.
J ¼ 13.0 Hz, 1H, CH), 8.38 (d, J ¼ 8.4 Hz, 2H, 2 ꢀ AreH), 8.17 (d,
J ¼ 7.3 Hz, 2H, 2 ꢀ AreH), 7.93 (d, J ¼ 8.7 Hz, 2H, 2 ꢀ AreH), 7.85 (t,
J ¼ 7.7 Hz, 2H, 2 ꢀ AreH), 7.80 (d, J ¼ 7.4 Hz, 2H, 2 ꢀ AreH), 7.60 (t,
J ¼ 7.6 Hz, 2H, 2 ꢀ AreH), 7.10 (d, J ¼ 13.0 Hz, 2H, 2 ꢀ CH), 4.47 (q,
J ¼ 6.8 Hz, 4H, 2 ꢀ CH2), 1.41 (t, J ¼ 7.0 Hz, 6H, 2 ꢀ CH3). 13C NMR
(151 MHz, DMSO)
d 148.30, 142.51, 140.28, 137.71, 132.61, 125.74,
124.86, 124.13, 117.15, 110.40, 108.71, 48.35, 14.47. MS (ESIþ) m/z:
2.3. Synthesis
calcd for C25H24Nþ2 : 353.2018, found: 353.2017 [M-Iꢁ]þ.
2.3.1. Synthesis of 1-ethyl-4-methylquinolin-1-ium iodide (1a) and
1-ethyl-4-(2-(N-phenyl- acetamido)vinyl)quinolin-1-ium iodide
(2a)
Compounds 1a and 2a were prepared according to the reported
procedures [18].
2.3.5. Synthesis of 1-decyl-4-(3-(1-decylquinolin-4(1H)-ylidene)
prop-1-en-1-yl)quinolin-1-ium iodide (3b)
To a mixture of 2b (278.2 mg, 0.5 mmol) and 1b (205.6 mg,
0.5 mmol) in ethanol (5.0 mL), Et3N (0.15 mL) was added in por-
tions, and then the mixture was refluxed for 1 h. The reactant was
cooled to room temperature, and ethyl ether (30 mL) was added.
The product was collected by filtration and purified by column
chromatography eluting with dichloromethane and acetone
(v:v ¼ 2:1) to give the target product as a dark green solid. Yield:
2.3.2. Synthesis of 1-decyl-4-methylquinolin-1-ium iodide (1b)
A solution of 4-methylquinoline (2.00 g, 14.0 mmol) and 1-
iododecane (4.50 g, 16.8 mmol) in acetonitrile (140 mL) was
refluxed for 48 h under nitrogen atmosphere. The solvent was
removed under reduced pressure and the residue was purified by
column chromatographyeluting with dichloromethane and acetone
(v:v ¼ 2:1) to give the brown liquid product. Yield: 51.5%; 1H NMR
58.5%. mp 155.1e156.0 ꢂC. 1H NMR (400 MHz, CDCl3)
d 8.41 (t,
J ¼ 12.9 Hz, 1H, CH), 8.23 (d, J ¼ 8.2 Hz, 2H, 2 ꢀ AreH), 7.79 (d,
J ¼ 7.3 Hz, 2H, 2 ꢀ AreH), 7.73 (d, J ¼ 7.5 Hz, 2H, 2 ꢀ AreH), 7.66 (t,
J ¼ 7.8 Hz, 2H, 2 ꢀ AreH), 7.49 (d, J ¼ 8.7 Hz, 2H, 2 ꢀ AreH), 7.44 (t,
J ¼ 7.5 Hz, 2H, 2 ꢀ AreH), 6.86 (d, J ¼ 13.0 Hz, 2H, 2 ꢀ CH), 4.18 (t,
J ¼ 7.3 Hz, 4H, 2 ꢀ CH2), 1.87e1.73 (m, 4H, 2 ꢀ CH2), 1.45e1.12 (m,
28H, 14 ꢀ CH2), 0.86 (t, J ¼ 6.8 Hz, 6H, 2 ꢀ CH3). 13C NMR (75 MHz,
(400 MHz, CDCl3)
d
10.15 (d, J ¼ 6.0 Hz,1H, AreH), 8.39 (d, J ¼ 8.7 Hz,
2H, 2 ꢀ AreH), 8.30e8.15 (m, 2H, 2 ꢀ AreH), 8.04 (d, J ¼ 6.1 Hz, 1H,
AreH), 8.01 (dd, J ¼ 8.2, 7.3 Hz,1H, AreH),, 5.27 (t, J ¼ 7. Hz, 2H, CH2),
3.03 (s, 3H, CH3), 2.17e2.02 (m, 2H, CH2), 1.56e1.45 (m, 2H, CH2),
1.40e1.31 (m, 2H, CH2),1.31e1.18 (m,10H, 5 ꢀ CH2), 0.86 (t, J ¼ 6. Hz,
CDCl3)
d 148.73, 142.46, 140.08, 137.97, 132.32, 125.55, 124.75,
116.19, 110.69, 109.97, 54.45, 31.84, 29.48, 29.44, 29.25, 29.23, 29.11,
26.74, 22.66, 14.11. MS(ESIþ) m/z: calcd for C41H57Nþ2 : 577.4522,
found: 577.4531 [M-Iꢁ]þ.
3H, CH3). 13C NMR (75 MHz, CDCl3)
d 158.34, 148.43, 136.99, 135.86,
130.26, 129.49, 127.14, 123.20, 119.17, 58.15, 31.78, 30.22, 29.44,
29.34, 29.19, 29.13, 26.49, 22.60, 20.87,14.09. MS (ESIþ) m/z: calcd for
C20H30Nþ: 284.2378, found: 284.2378 [M-Iꢁ]þ.
2.4. Spinning coating of the film
2.3.3. Synthesis of 1-decyl-4-(2-(N-phenylacetamido)vinyl)
quinolin-1-ium iodide (2b)
The quartz glass (25 ꢀ 25 ꢀ 1 mm3) was sequentially washed
with distilled water, acetone, ethanol and then acetone in an ul-
trasonic bath. Dye 3b (20.0 mg) was dissolved in cyclopentanone
Compound 1b (1.65 g, 4.0 mmol) was reacted with N,N0-
diphenylformamidine (0.79 g, 4.0 mmol) at 165 ꢂC for 30 min, the
residue product was washed with diethyl ether and ethanol
sequentially, then dried under reduced pressure. Acetic anhydride
(3 mL) and triethyl orthoformate (1.5 mL) were added to the above
residue and the resultant suspension was stirred at 100 ꢂC for
15 min. The reactant was cooled to room temperature, diethyl ether
(20 mL) was added slowly. The product was collected by filtration
and finally purified by column chromatography eluting with
dichloromethane and acetone (v:v ¼ 2:1) to give the product as a
yellow solid. Yield: 30.6%; mp 143.2e144.5 ꢂC; 1H NMR (400 MHz,
(1.0 mL). The solution, which was filtered through a 0.22 mm filter,
was subsequently spinecoated at 1300 rmp on a quartz glass and
the film was dried in a vacuum oven at 60 ꢂC for 24 h to remove the
residual solvent.
3. Results and discussion
3.1. Preparation of the materials
The synthetic schedule is shown in Fig. 1. Compounds 1aeb
were synthesized by the alkylation of the 4-methylquinoline. The
intermediates (2aeb) can be obtained by the one [19] or two steps
[18] synthesis according to the reported methods, and the two
steps synthesis was adopted for 2aeb since the procedures are
more efficient for purification in this case. The final products (3ae
b) were prepared by the condensations between the 2ae2b and
CDCl3)
d
9.90 (d, J ¼ 6.3 Hz, 1H, AreH), 8.88 (d, J ¼ 14.1 Hz, 1H, Are
H), 8.19 (d, J ¼ 8.8 Hz, 1H, AreH), 8.16e8.02 (m, 2H, 2 ꢀ AreH), 7.88
(d, J ¼ 8.5 Hz,1H, CH), 7.76 (t, J ¼ 7.7 Hz, 1H, AreH), 7.66 (m, J ¼ 14.4,
7.3 Hz, 3H, 3 ꢀ AreH), 7.37 (d, J ¼ 7.3 Hz, 2H, 2 ꢀ AreH), 6.02 (d,
J ¼ 14.1 Hz, 1H, CH), 5.12 (t, J ¼ 7.4 Hz, 2H, CH2), 2.09 (s, 3H, CH3),
2.03 (m, 2H, CH2), 1.55e1.40 (m, 3H, CH3), 1.33 (m, J ¼ 5.7 Hz, 2H,