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LCs. Therefore, we report some E/Z isomerization studies of ¼ 6.9 Hz, Ph), 7.99 (d, 2H ꢂ 6, J ¼ 6.8 Hz, Ph), 7.05 (d, 2H ꢂ 6, J
these unconventional azobenzene compounds for possible ¼ 8.6 Hz, Ph), 5.89 (m, 1H ꢂ 6), 5.13 (d, 1H ꢂ 6, J ¼ 16.5 Hz),
applications in optical data storage and molecular switches.
5.05 (d, 1H ꢂ 6, J ¼ 9.9 Hz), 4.09 (t, 2H ꢂ 6, J ¼ 6.7 Hz, OCH2–),
3.97 (s, 6H, core), 2.29 (m, 2H ꢂ 6, –CH2), 2.08 (m, 2H ꢂ 6,
–CH2–), 1.96 (m, 2H ꢂ 6, –CH2–). dC (125 MHz; CDCl3; Me4Si)
26.11, 29.80, 33.90, 69.01, 72.60, 115.33, 118.45, 122.42, 125.31,
130.61, 131.55, 132.72, 147.13, 155.23, 162.36, 164.40.
Elemental analysis, found: C, 71.19; H, 6.10; N, 8.20%. Calc. for
2. Experimental
2.1 Synthesis of intermediate compounds
All intermediate compounds 1, 2a–e and 3a–e were synthesized
according to our earlier papers.30,39
C
120H120N12O18: C, 71.41; H, 6.01; N, 8.32%.
2.2 1,2,3,4,5,6-Hexakis[4-{[4-(but-3-en-1-yloxy)phenyl]-
diazenyl}benzoate]cyclohexane (4a)
2.5 1,2,3,4,5,6-Hexakis[4-{[4-(hept-6-en-1-yloxy)phenyl]-
diazenyl}benzoate]cyclohexane (4d)
Compound 3a (40 mg, 0.135 mmol), 25 mL of dry dichloro-
methane, DMAP (4.0 mg, 0.03 mmol), myo-inositol (4.0 mg,
0.0223 mmol) and DCC (44 mg, 0.20 mmol) were mixed and the
mixture was stirred for 24 h. Work-up procedure was according
to our previous report.30 Yield of 4a: 0.015 g (31%). IR, nmax/cmꢁ1
3072 (]CH2), 2922 (CH2), 2852 (CH2), 1720 (C]O, ester), 1670
(C]C, vinyl), 1647, 1456 (C]C, aromatic), 1269, 1141, 1028 (C–
O), 891 (C–H). dH (500 MHz; CDCl3; Me4Si) 8.35 (d, 2H ꢂ 6, J ¼
8.9 Hz, Ph), 8.00 (d, 2H ꢂ 6, J ¼ 8.2 Hz, Ph), 7.95 (d, 2H ꢂ 6, J ¼
8.9 Hz, Ph), 7.05 (d, 2H ꢂ 6, J ¼ 8.9 Hz, Ph), 5.95 (m, 1H ꢂ 6,
CH]), 5.25 (d, 1H ꢂ 6, J ¼ 16.5 Hz, ]CH2), 5.16 (d, 1H ꢂ 6, J ¼
9.9 Hz, ]CH2), 4.14 (t, 2H ꢂ 6, J ¼ 6.8 Hz, OCH2–), 3.98 (s, 6H,
core), 2.63 (m, 2H ꢂ 6, –CH2–). dC (125 MHz; CDCl3; Me4Si)
34.20, 68.60, 72.60, 115.18, 118.25, 122.41, 125.24, 130.64,
131.66, 132.73, 147.23, 155.38, 162.38, 164.44. Elemental anal-
ysis, found: C, 70.01; H, 5.12; N, 8.99%. Calc. for C108H96N12O18:
C, 70.11; H, 5.23; N, 9.08%.
Compound 4d was synthesized from 3d according to the
procedure described for the synthesis of 4a. Yield of 4d: 0.016 g
(32%). IR, nmax/cmꢁ1 3061 (]CH2), 2922 (CH2), 2854 (CH2),
1722 (C]O, ester), 1643 (C]C, vinyl), 1602, 1456 (C]C,
aromatic), 1282, 1107, 1030 (C–O), 840 (C–H). dH (500 MHz;
CDCl3; Me4Si) 8.35 (d, 2H ꢂ 6, J ¼ 8.2 Hz, Ph), 8.01 (d, 2H ꢂ 6, J
¼ 6.9 Hz, Ph), 7.93 (d, 2H ꢂ 6, J ¼ 6.8 Hz), 7.04 (d, 2H ꢂ 6, J ¼
8.6 Hz, Ph), 5.85 (m, 1H ꢂ 6), 5.07 (d, 1H ꢂ 6, J ¼ 16.5 Hz), 4.99
(d, 1H ꢂ 6, J ¼ 9.9 Hz), 4.08 (t, 2H ꢂ 6, J ¼ 6.7 Hz, OCH2–), 3.98
(s, 6H, core), 2.12 (m, 2H ꢂ 6, –CH2–), 1.97 (m, 2H ꢂ 6, –CH2–),
1.86 (m, 2H ꢂ 6, –CH2–), 1.70 (m, 2H ꢂ 6, –CH2–). dC (125 MHz;
CDCl3; Me4Si) 25.91, 27.78, 29.80, 34.01, 69.01, 72.60, 115.65,
118.44, 122.33, 125.35, 130.55, 131.67, 132.47, 147.26, 155.43,
162.37, 164.43. Elemental analysis, found: C, 71.83; H, 6.13; N,
7.85%. Calc. for C126H132N12O18:C, 71.97; H, 6.04; N, 7.99%.
2.6 1,2,3,4,5,6-Hexakis[4-{[4-(oct-7-en-1-yloxy)phenyl]-
diazenyl}benzoate]cyclohexane (4e)
2.3 1,2,3,4,5,6-Hexakis[4-{[4-(pent-4-en-1-yloxy)phenyl]-
diazenyl}benzoate]cyclohexane (4b)
Compound 4e was synthesized from 3e according to the
procedure described for the synthesis of 4a. Yield of 4e: 0.017 g
(31.5%). IR, nmax/cmꢁ1 3074 (]CH2), 2924 (CH2), 2852 (CH2),
1722 (C]O, ester), 1643 (C]C, vinyl), 1602, 1458 (C]C,
aromatic), 1281, 1143, 1028 (C–O), 840 (C–H). dH (500 MHz;
CDCl3; Me4Si) 8.21 (d, 2H ꢂ 6, J ¼ 8.2 Hz, Ph), 7.97 (d, 2H ꢂ 6, J
¼ 6.9 Hz, Ph), 7.92 (d, 2H ꢂ 6, J ¼ 6.8 Hz, Ph), 7.03 (d, 2H ꢂ 6, J
¼ 8.6 Hz, Ph), 5.85 (m, 1H ꢂ 6), 5.05 (d, 1H ꢂ 6, J ¼ 16.5 Hz),
4.96 (d, 1H ꢂ 6, J ¼ 9.9 Hz), 4.08 (t, 2H ꢂ 6, J ¼ 6.7 Hz, OCH2–),
3.98 (s, 6H, core), 2.11 (m, 2H ꢂ 6, –CH2–), 1.85 (m, 2H ꢂ 6,
–CH2–), 1.49 (m, 2H ꢂ 6, –CH2–), 1.44 (m, 4H ꢂ 6, –CH2–). dC
(125 MHz; CDCl3; Me4Si) 25.24, 27.28, 29.12, 30.23, 34.21, 69.01,
72.60, 115.66, 118.34, 122.78, 125.33, 130.68, 131.69, 132.89,
147.27, 155.48, 162.33, 164.44. Elemental analysis, found: C,
72.39; H, 6.50; N, 7.52%. Calc. for C132H144N12O18: C, 72.50; H,
6.63; N, 7.68%.
Compound 4b was synthesized from 3b according to the
procedure described for the synthesis of 4a. Yield of 4b: 0.018 g
(35%). IR, nmax/cmꢁ1 3076 (]CH2), 2924 (CH2), 2852 (CH2),
1718 (nC]O, ester), 1645 (C]C, vinyl), 1626, 1456 (C]C,
aromatic), 1257, 1143, 1087 (C–O), 842 (C–H). dH (500 MHz;
CDCl3; Me4Si) 8.36 (d, 2H ꢂ 6, J ¼ 8.7 Hz, Ph), 8.01 (d, 2H ꢂ 6, J
¼ 8.3 Hz, Ph) 7.99 (d, 2H ꢂ 6, J ¼ 8.9 Hz, Ph), 7.05 (t, 2H ꢂ 6, J ¼
8.3 Hz, Ph), 5.88 (m, 1H ꢂ 6, CH]), 5.10 (d, 1H ꢂ 6, J ¼ 9.8 Hz,
]CH2), 5.03 (d, 1H ꢂ 6, J ¼ 9.9 Hz, ]CH2), 4.09 (t, 2H ꢂ 6, J ¼
6.7 Hz, OCH2–), 3.97 (s, 6H, core), 2.30 (m, 2H ꢂ 6, –CH2), 1.97
(m, 2H ꢂ 6, –CH2–). dC (125 MHz; CDCl3; Me4Si) 29.00, 30.20,
69.00, 72.60, 115.23, 118.75, 122.65, 125.41, 130.48, 131.83,
132.66, 147.45, 155.56, 162.34, 164.42. Elemental analysis,
found: C, 70.89; H, 6.15; N, 8.61%. Calc. for C114H108N12O18: C,
70.97; H, 6.25; N, 8.69%.
3. Instruments
2.4 1,2,3,4,5,6-Hexakis[4-{[4-(hex-5-en-1-yloxy)phenyl]-
diazenyl}benzoate]cyclohexane (4c)
IR spectra were recorded with a Perkin Elmer (670) FTIR spec-
1
Compound 4c was synthesized from 3c according to the trometer. H NMR (500 MHz) and 13C NMR (125 MHz) spectra
procedure described for the synthesis of 4a. Yield of 4c: 0.020 g were recorded with a Bruker (DMX500) spectrometer. The
(37%). IR, nmax/cmꢁ1 3072 (]CH2), 2922 (CH2), 2852 (CH2), transition temperatures and their enthalpies were measured by
1718 (C]O, ester), 1643 (C]C, vinyl), 1626, 1454 (C]C, differential scanning calorimetry (Perkin DSC 7) with heating
aromatic), 1246 1143, 1045 (C–O), 860 (C–H). dH (500 MHz; and cooling rates of 10 ꢃC minꢁ1. Optical textures were obtained
CDCl3; Me4Si) 8.36 (d, 2H ꢂ 6, J ¼ 8.2 Hz, Ph), 8.01 (d, 2H ꢂ 6, J using an Olympus BX51 polarizing optical microscope
35090 | RSC Adv., 2014, 4, 35089–35098
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