Paper
Journal of Materials Chemistry C
The good NLO performance is due to the utilization of the ( yield 70.0%). 1H NMR (300 MHz, CDCl3, 298 K), d (TMS, ppm):
chromophore with a high mb value (the mb value of FTC is 31 8.96–8.91 (d, J = 15.3 Hz, H, –CHQ), 8.01–7.99 (m, 4H, ArH),
times that of the azo chromophore and the mass fraction of the 7.94–7.91 (m, 2H, ArH), 7.87–7.82 (m, 3H, ArH, –CHQ), 7.68–
FTC part of M1 is 37.2%) and appropriate molecular design 7.65 (m, H, ArH), 7.59–7.54 (m, 2H, ArH), 7.45–7.37 (m, 7H, ArH),
(the structure of M1 is like an ‘‘H’’). So this work has achieved 7.26 (m, H, ArH), 7.12–6.97 (m, 4H, ArH, –CHQ), 6.66 (m, 3H,
the expected results.
–CHQ, ArH), 4.58–4.56 (m, 4H, –CH2–), 4.41 (m, 2H, –CH2–),
4.34 (m, 2H, –CH2–), 4.28–4.26 (m, 2H, –CH2–), 3.95 (m, 4H,
–CH2–), 3.41 (m, 4H, –CH2–), 3.02–2.98 (m, 2H, –CH2–), 2.35–2.31
(m, 2H, –CH2–), 1.96 (m, 4H, –CH2–), 1.78 (s, 6H, –CH3), 1.22
(m, 6H, –CH3). 13C NMR (75 MHz, CDCl3, 298 K), d (ppm):
175.87, 173.98, 166.39, 155.11, 152.96, 150.79, 148.76, 148.23,
147.00, 146.82, 144.90, 142.63, 140.02, 135.52 133.22, 132.16,
129.53, 129.15, 128.42, 126.12, 125.79, 122.56, 122.47, 121.37,
117.36, 116.38, 114.72, 112.40, 111.87, 111.73, 111.52, 109.22,
97.40, 68.74, 61.63, 49.82, 49.55, 49.04, 44.42, 28.34, 26.94, 26.84,
26.44, 21.84, 12.57. C69H66N14O8S (EA) (%, found/calcd): C, 66.13/
66.22; H, 5.35/5.32; N, 15.83/15.67; S, 2.77/2.56. HR-ESI-MS: m/z for
C69H66N14O8S (found/calcd): [M + H]+: 1251.4984/1251.4982.
M2. Similar to the preparation of M1, M2 was synthesized
from FTC-2 and compound E as a dark powder (63 mg, 64.7%).
1H NMR (300 MHz, CDCl3, 298 K), d (TMS, ppm): 8.01–7.99
(m, 4H, ArH), 7.93–7.86 (m, 4H, ArH), 7.79–7.74 (m, 2H,
ArH, –CHQ), 7.68–7.65 (m, H, ArH), 7.59–7.54 (m, 2H, ArH),
7.45–7.40 (m, 5H, ArH, –CHQ), 7.34–7.29 (m, 3H, ArH), 7.21
(1, H, –CHQ), 7.04–6.95 (m, 3H, ArH, –CHQ), 6.58–6.49 (m,
3H, –CHQ, ArH), 4.59–4.55 (m, 4H, –CH2–), 4.48–4.46 (m, 2H,
–CH2–), 4.12–4.08 (m, 2H, –CH2–), 3.96–3.92 (m, 4H, –CH2–),
3.80 (m, 2H, –CH2–), 3.22–3.20 (m, 2H, –CH2–), 2.99–2.95
(m, 2H, –CH2–), 2.26–2.22 (m, 2H, –CH2–), 1.75 (s, 6H, –CH3),
1.08–1.03 (t, J = 7.5 Hz, 3H, –CH3). 13C NMR (75 MHz, CDCl3,
298 K), d (ppm): 172.91, 166.39, 155.08, 153.74, 150.75,
148.26, 147.80, 146.87, 146.81, 144.93, 139.27, 137.51, 137.40,
134.03, 133.24, 129.52, 129.46, 128.89, 128.52, 128.47, 127.10,
126.12,124.25, 122.35, 117.41, 116.40, 112.14, 111.84, 111.43,
110.93, 109.26, 96.98, 68.61, 61.60, 50.24, 49.81, 47.96, 45.14,
28.43, 26.39, 21.67, 11.95. C63H57N11O8S (EA) (%, found/calcd):
C, 66.99/67.07; H, 5.10/5.09; N, 13.64/13.66; S, 2.97/2.84.
HR-ESI-MS: m/z for C63H57N11O8S (found/calcd): [M + H]+:
1128.4191/1128.4185.
Experimental section
Materials and instrumentation
Tetrahydrofuran (THF) was dried over and distilled from K–Na
alloy under an atmosphere of dry nitrogen. Dichloromethane
and N,N-dimethylformamide (DMF) were dried over and distilled
from CaH2. Anhydrous ethanol were dried over and distilled from
sodium metallic. Compounds A and B, and TCF were synthesized
according to the literature method.12d Compound E and com-
pound F were synthesized according to our previous work
through similar synthetic routes,5c,13a and the detailed syn-
thetic procedure is listed in the ESI† (Scheme S1). All other
reagents were used as received.
1H and 13C NMR spectra were measured on a Varian
Mercury300 spectrometer using tetramethylsilane (TMS; d = 0
ppm) as an internal standard. The Fourier transform infrared
(FTIR) spectra were recorded on a PerkinElmer-2 spectrometer
in the region of 3000–500 cmÀ1. UV-visible spectra were
obtained using a Shimadzu UV-2550 spectrometer. Matrix-
assisted laser desorption ionization time-of-flight mass spectra
were recorded on a Voyager-DE-STR MALDI-TOF mass spectro-
meter (MALDI-TOF MS; ABI, American) equipped with a 337 nm
nitrogen laser and a 1.2 m linear flight path in positive
ion mode. Elemental analyses (EA) were performed using a
CARLOERBA-1106 microelemental analyzer. Thermogravimetric
analysis (TGA) was performed on a NETZSCH STA449C thermal
analyzer at a heating rate of 10 1C minÀ1 under nitrogen at a flow
rate of 50 cm3 minÀ1. The thermal transitions were investigated
using a METTLER differential scanning calorimeter DSC822e
under nitrogen at a scanning rate of 10 1C minÀ1. The thickness
of the films was measured with an Ambios Technology XP-2
profilometer.
M3. Similar to the preparation of M1, M3 was synthesized
from FTC-3 and compound E as a dark powder (54 mg, 75.5%).
1H NMR (300 MHz, CDCl3, 298 K), d (TMS, ppm): 8.02–7.99
Synthesis
The synthetic routes of four derivatives of FTC (named FTC-1 to (m, 8H, ArH), 7.94–7.87 (m, 8H, ArH), 7.79–7.74 (m, 3H, ArH,
FTC-4) are listed in the ESI.† The synthetic routes of five target –CHQ), 7.68–7.65 (m, 2H, ArH), 7.59–7.54 (m, 4H, ArH),
products are shown as follows.
7.45–7.40 (m, 8H, ArH, –CHQ), 7.33–7.26 (m, 3H, ArH,
M1. Under an atmosphere of dry nitrogen, a solution of FTC-1 –CHQ), 7.04–6.95 (m, 7H, ArH, –CHQ), 6.56–6.53 (m, 3H,
(64.4 mg, 0.098 mmol), compound E (61 mg, 0.098 mmol), –CHQ, ArH), 4.57 (m, 8H, –CH2–), 4.27–4.25 (m, 8H, –CH2–),
copper sulfate pentahydrate (2.4 mg, 10% mmol), sodium bicar- 3.95 (m, 8H, –CH2–), 3.23(m, 4H, –CH2–), 3.02–2.98 (m, 4H,
bonate (1.7 mg, 20% mmol), and sodium L-ascorbate (3.5 mg, –CH2–), 2.33–2.31 (m, 4H, –CH2–), 1.84 (m, 2H, –CH2–), 1.74
20% mmol) in 3/0.6 mL of THF/H2O was stirred at 28–30 1C for (s, 6H, –CH3), 1.59 (m, 4H, –CH2–), 1.30 (m, 10H, –CH2–).
3 h. Then the reaction mixture was poured into water and 13C NMR (75 MHz, CDCl3, 298 K), d (ppm): 174.27, 166.36,
extracted with CH2Cl2 three times (50 mL Â 3). The combined 155.12, 150.79, 148.21, 146.87, 146.70, 144.91, 142.64, 139.64,
organic solution was dried over anhydrous sodium sulfate and 133.20, 129.51, 128.40, 126.11, 122.66, 121.14, 121.02, 117.37,
condensed via rotary evaporation. The residue was purified by 116.36, 111.87, 109.24, 68.79, 68.70, 61.63, 50.08, 49.79, 49.66,
column spectroscopy on silica gel using the solvents of CH2Cl2 29.76, 29.69, 28.42, 26.50, 26.27, 25.54, 21.86. C106H104N18O15S
and ethyl acetate (2 : 1) as an eluent to give 85 mg of the product (EA) (%, found/calcd): C, 66.94/66.93; H, 5.49/5.51; N, 13.30/13.25;
This journal is ©The Royal Society of Chemistry 2016
J. Mater. Chem. C, 2016, 4, 11474--11481 | 11479