Journal of Materials Chemistry A
Paper
as it is widely used in industry because its reduction product, the reaction mixture was reuxed overnight. Chlorobenzene
p-phenylenediamine, is used in the preparation of azo dyes, fur was then removed under vacuum, and the residue so obtained
dyes, polymers, rubber antioxidants and photo-developers.20 was treated with water, extracted with 50 ml of dichloro-
The catalytic activity of these nanomaterials is much better than methane, and dried over anhydrous Na2SO4. The organic layer
the catalytic activity of the systems reported in the literature for was evaporated, and the compound was puried by column
this type of reduction (see pS3 in the ESI†).
chromatography using (80 : 20) (chloroform : hexane) as an
eluent to give 0.178 g (30%) of compound 4 as a yellowish
orange solid; m.p. >260 ꢀC; 1H NMR (300 MHz, CDCl3): d ¼ 7.32
[d, 4H, J ¼ 8.1 Hz, ArH], 7.63 [d, 4H, J ¼ 8.7 ArH], 7.78–7.81 [m,
2H, ArH], 8.08–8.10 [m, 2H, ArH], 8.12 [s, 2H, ArH], 8.77 [s, 2H,
ArH]; 8.81 [s, 2H, ArH]; 13C NMR (75.45 MHz, CDCl3): 82.31,
112.00, 113.35, 118.23, 126.17, 127.82, 128.70, 129.18, 129.42,
130.40, 130.65, 131.12, 132.31, 132.76, 133.43, 141.09, 143.72,
158.04, 161.18; TOF MS ES+: 629.14 (M + Na)+; elemental anal-
ysis: calcd for C42H18N6: C 83.16; H 2.99; N 13.85; found: C
83.11; H 2.90; N 13.79%.
2. Experimental section
2.1. Materials
All reagents were purchased from Aldrich and were used
without further purication. THF was dried over sodium and
benzophenone and kept over molecular sieves overnight
before use. Silica gel (60–120 mesh) was used for column
chromatography.
Compound 5. To a solution of 1 (0.5 g, 1.07 mmol) and 2a
(0.72 g, 2.25 mmol) in 1,4-dioxane (20 ml) were added K2CO3
(1.18 g, 8.56 mmol), distilled H2O (3 ml), and [Pd(PPh3)4] (0.273 g,
0.236 mmol) under N2, and the reaction mixture was reuxed
overnight. 1,4-Dioxane was then removed under vacuum, and the
residue so obtained was treated with water, extracted with
dichloromethane, and dried over anhydrous Na2SO4. The organic
layer was evaporated, and the compound was puried by column
chromatography using 1 : 1 (chloroform : hexane) as an eluent to
give 0.248 g (35%) of compound 5 as a yellow solid; m.p. >260 ꢀC;
1H NMR (300 MHz, CDCl3): d ¼ 0.92 [t, 6H, J ¼ 6.6 Hz,
OCH2CH2(CH2)3CH3], 1.26 [br, 4H, OCH2CH2CH2CH2CH2CH3],
1.35–1.37 [m, 4H, OCH2CH2CH2CH2CH2CH3], 1.48–1.55 [m, 4H,
2.2. Instruments
UV-vis spectra were recorded on a SHIMADZU UV-2450 spec-
trophotometer, with a quartz cuvette (path length, 1 cm). The
cell holder was thermostatted at 25 ꢀC. Fluorescence spectra
were recorded with a SHIMADZU 5301 PC spectrouorimeter.
Scanning electron microscopy (SEM) images were obtained with
a eld-emission scanning electron microscope (SEM CARL
ZEISS SUPRA 55). Polarized optical microscopy (POM) images
were recorded on a NIKON ECLIPSE LV100 POL. Elemental
analysis (C, H, N) was performed on a Flash EA 1112 CHNS-O
1
analyzer (Thermo Electron Corp.). H NMR spectra were recor-
ded on a JEOL-FT NMR-AL 300 MHz spectrophotometer using
CDCl3 as solvent and tetramethylsilane SiMe4 as internal stan-
dard. UV-vis studies were performed in THF and H2O–THF
mixture. Data are reported as follows: chemical shis in ppm
(d), multiplicity (s ¼ singlet, d ¼ doublet, br ¼ broad singlet, m
¼ multiplet), coupling constant J (Hz), integration, and
interpretation.
OCH2CH2CH2CH2CH2CH3], 1.79 [t, 4H,
J
¼
7.35 Hz,
OCH2CH2(CH2)3CH3], 3.97 [t, 4H, J ¼ 6.6 Hz, OCH2CH2-
(CH2)3CH3], 6.83 [d, 4H, J ¼ 8.7 Hz, ArH], 7.16 [d, 4H, J ¼ 8.7 ArH],
7.69–7.72 [m, 2H, ArH], 8.09 [s, 2H, ArH], 8.11–8.15 (m, 2H, ArH),
8.94 [s, 2H, ArH], 8.95 (s, 2H, ArH); 13C-NMR d (75.45 MHz,
CDCl3): 14.04, 22.62, 25.76, 29.27, 31.62, 68.04, 99.99, 114.22,
129.47, 129.78, 130.12, 130.60, 130.69, 130.95, 131.14, 132.63,
134.40, 135.27, 142.75, 158.55, 182.94; TOF MS ES+: 685.4335 (M
2.3. Synthesis
Compound 3. To a solution of 1 (0.50 g, 1.07 mmol) and 2 + Na + 2)+; elemental analysis: calcd for C46H44O4: C 83.60; H 6.71;
(0.33 g, 2.25 mmol) in 1,4-dioxane (20 ml) were added K2CO3 found: C 83.55; H 6.60%.
(0.89 g, 6.42 mmol), distilled H2O (2.10 ml), and [Pd(PPh3)4]
Compound 6. To a mixture of 5 (0.1 g, 0.151 mmol) in 10 ml
(0.27 g, 0.24 mmol) under N2, and the reaction mixture was dry pyridine were added 0.2 ml of TiCl4 and malononitrile
reuxed overnight. 1,4-Dioxane was then removed under (0.199 g, 3.02 mmol) under N2, and the reaction mixture was
vacuum, and the residue so obtained was treated with water, reuxed overnight. Aer that the reaction mixture was allowed
extracted with dichloromethane, and dried over anhydrous to cool to room temperature. The mixture was then diluted with
Na2SO4. The organic layer was evaporated, and the compound dichloromethane and washed with water in 2 N HCl. The
was puried by column chromatography using 80 : 20 (chlor- organic layer was separated and dried over anhydrous Na2SO4.
oform : hexane) as an eluent to give 0.191 g (35%) of compound The solvent was evaporated under reduced pressure to get the
3 as a yellow solid; m.p. >260 ꢀC; 1H NMR (300 MHz, CDCl3): d ¼ crude product. The crude product was puried by column
7.35 [d, 4H, J ¼ 8.1 Hz, ArH], 7.63 [d, 4H, J ¼ 8.1 Hz, ArH], 7.73– chromatography using 1 : 1 (hexane : chloroform) as an eluent
7.76 [m, 2H, ArH], 8.14–8.18 [m, 2H, ArH], 8.19 [s, 2H, ArH], 8.98 to give 0.246 g (43%) compound 6 as a red solid; m.p. >260 ꢀC;
[s, 2H, ArH]; 9.03 [s, 2H, ArH]; TOF MS ES+: 511.0320; elemental 1H NMR (400 MHz, CDCl3): d ¼ 0.85 [t, 6H, J ¼ 6.0 Hz,
analysis: calcd for C36H18N2O2: C 84.69; H 3.55; N 5.49; found: C OCH2CH2(CH2)3CH3], 1.18 [br, 4H, OCH2CH2CH2CH2CH2CH3],
84.32; H 3.49; N 5.39%. Due to the poor solubility of compound 1.28–1.29 [m, 4H, OCH2CH2CH2CH2CH2CH3], 1.40 [br, 4H,
3, its 13C NMR spectrum could not be recorded.
Compound 4. To a solution of 3 (0.50 g, 0.98 mmol) and OCH2CH2(CH2)3CH3], 3.89 [t, 4H,
malononitrile (0.76 g, 19.60 mmol) in 50 ml dry chlorobenzene (CH2)3CH3], 6.75 [d, 4H, J ¼ 8 Hz, ArH], 7.07 [d, 4H, J ¼ 8 Hz,
were added 0.75 ml pyridine and 0.50 ml of TiCl4 under N2, and ArH], 7.68–7.70 [m, 2H, ArH], 7.94 [s, 2H, ArH], 7.98–8.00
OCH2CH2CH2CH2CH2CH3], 1.72 [t, 4H,
J
¼
8
Hz,
J
¼
6 Hz, OCH2CH2-
8370 | J. Mater. Chem. A, 2014, 2, 8369–8375
This journal is © The Royal Society of Chemistry 2014