Bent-core liquid crystal (LC) decorated gold nanoclusters: Synthesis, self-assembly, and effects in mixtures with bent-core LC hosts

Article abstract of DOI:10.1039/b802554a

We present the first synthesis of a series of thiol-, thioacetate-, and xanthate-terminated bent-core derivatives, as well as the preparation of gold nanoclusters using the thiol-terminated bent-core compounds. The mesomorphic properties of the bent-core compounds have been investigated by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), small angle X-ray scattering (SAXS), and electro-optic tests. From this series, the mono-xanthate derivatives form rectangular or hexagonal columnar phases, and the mono-thiol derivative with shorter alkyl chains forms a metastable, likely smectic, phase. All other bent-core compounds and intermediates exclusively form disordered or multi-layer lamellar crystalline solid modifications. High-resolution transmission electron microscopy (HR-TEM) images of the bent-core functionalized gold nanoclusters prepared from the thiol-terminated derivatives, taken after slow evaporation of the solvent, provide evidence for the formation of self-assembled nanocluster arrays. Upon dispersion of these gold nanoclusters in two structurally related bent-core LC hosts (one forming a SmCP_A, and the second with a terminal double bond displaying a Col_r phase), a shift in the surface plasmon resonance was observed indicating a LC host-dependent aggregation of the nanoparticles. Finally, we report initial results on the effects of different concentrations of these nanoclusters on the thermal properties as well as the applied voltage/current response of the parent SmCP_A host.

Full text of DOI:10.1039/b802554a

Supplementary material (ESI) for Journal of Materials Chemistry
This journal is © The Royal Society of Chemistry 2008
Bent-core LC decorated gold nanoclusters: Synthesis, self-assembly, and
effects in mixtures with bent-core LC hosts
Vanessa M. Marx,a Hidy Girgis,a Paul A. Heiney b and Torsten Hegmann*a
Contents:
1. Detailed synthetic information
S
2
2
1.1 General Considerations
1.2 Intermediates
2
1.3 Final bent-core compounds
1.4 Bent-core decorated Au nanoparticles
2. POM images of selected bent-core derivatives
2.1 BC3
7
11
12
12
13
13
14
15
16
17
18
2.2 BC9
2.3 BC14
3. 1H NMR spectra of Au1 and Au2
4. UV-visible spectra of Au1 and Au2
5. DSC traces of BC9 and BC14
6. DSC traces of Au1/BC1 and Au1/BC8 composites
7. POM images of BC1 doped with 5wt% Au1
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Supplementary material (ESI) for Journal of Materials Chemistry
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1. Detailed Synthetic Information
1.1 General Considerations. All reagents used were purchased from Sigma Aldrich and used as
received. All solvents used were Aldrich Purification grade, purified via a PureSolv solvent purification
system (Innovative Technology Inc.), with the exception of t-butanol (Alfa Aesar, 99%) and ethanol
(technical grade). All reactions were conducted under N2 atmosphere, unless stated otherwise. Yields
given as quantitative in the experimental procedures indicate yields of ‘crude’ intermediates, which did
not require column chromatography for purification, but showed sufficient purity by NMR.
1.2 Intermediates 1-25
Methyl 4-(decyloxy)benzoate (1). Anhydrous K2CO3 (18.43 g, 0.13 mol) was added to 300 mL of
CH3CN, and the solution was degassed with N2 for 20 minutes. Methyl-4-hydroxybenzoate (6.27 g,
41.2 mmol) was added to the reaction flask, which was heated to 70 °C, following which 1-
bromodecane (8.8 mL, 42.5 mmol) was added. The above solution was refluxed for 12 hours, and upon
cooling the solvent was removed under reduced pressure. The residue was taken in CH2Cl2 (200 mL)
and washed with 1 M HCl (100 mL). The organic layer was washed with distilled H2O (100 mL), and
1
the solvent was removed under reduced pressure. Yield 12.0 g (quant.). H NMR: δH (CDCl3; 300
MHz): 0.90 (3 H, t, 3J = 6.9 Hz, CH3), 1.24–1.54 (14 H, m, CH2), 1.81 (2 H, m, O-CH2-CH2), 3.90 (3
H, s, OCH3), 4.01 (2 H, t, 3J = 6.6 Hz, O-CH2), 6.92 (2 H, d, 3J = 9.0 Hz, Ar-H), 7.99 (2H, d, 3J = 9.0
Hz, Ar-H). 13C NMR: δC (CDCl3; 75 MHz): 14.5, 23.0, 26.4, 29.5, 29.7, 29.9, 32.3, 52.2, 68.6, 114.5,
122.7, 131.9, 163.4, 167.3.
Methyl 4-(dodecyloxy)benzoate (2). Synthesized as described above for compound 1. Quantities:
K2CO3 (8.63 g, 62 mmol), methyl-4-hydroxy-benzoate (4.75 g, 31 mmol), 1-bromododecane (7.6 mL,
32 mmol). Yield 9.58 g (96 %). 1H NMR: δH (CDCl3; 300 MHz): 0.88 (3 H, t, 3J = 6.9 Hz, CH3), 1.21–
3
1.51 (18 H, m, CH2), 1.79 (2 H, m, O-CH2-CH2), 3.88 (3 H, s, OCH3), 4.00 (2 H, t, J = 6.6 Hz, O-
3
3
13
CH2), 6.90 (2 H, d, J = 9.0 Hz, Ar-H), 7.98 (2 H, d, J = 9.0 Hz, Ar-H). C NMR: δC (CDCl3; 75
MHz): 14.5, 23.1, 26.4, 29.5, 29.8, 29.9, 30.0, 30.1, 32.3, 52.2, 68.6, 114.5, 122.7, 131.9, 163.4, 167.3.
1.3. Methyl 4-(dec-9-enyloxy)benzoate (3). Synthesized as described above for compound 1.
Quantities: K2CO3 (18.2 g, 0.13 mol), methyl-4-hydroxy-benzoate (6.30 g, 41.4 mmol), 10-bromo-1-
decene (8.6 mL, 42.8 mmol). Yield 12.0 g (quant.). 1H NMR: δH (CDCl3; 300 MHz): 1.23–1.51 (10 H,
m, CH2), 1.77 (2 H, m, O-CH2-CH2), 2.03 (2 H, m, CH2=CH-CH2), 3.85 (3 H, s, OCH3), 3.95 (2 H, t,
3J = 6.5 Hz, O-CH2), 4.95 (2 H, m, CH2=CH), 5.79 (1 H, m, CH2=CH), 6.87 (2 H, d, 3J = 9.0 Hz, Ar-
H), 7.98 (2 H, d, 3J = 9.0 Hz, Ar-H). 13C NMR: δC (CDCl3; 75 MHz): 26.0, 28.9, 29.0, 29.1, 29.3, 29.4,
51.7, 68.1, 114.0, 114.2, 122.3, 131.5, 139.0, 162.9, 166.7.
Methyl 4-(undec-10-enyloxy)benzoate (4). Synthesized as described above for compound 1.
Quantities: K2CO3 (9.08 g, 66 mmol), methyl-4-hydroxy-benzoate (5.00 g, 33 mmol), 11-bromo-1-
undecene (7.6 mL, 34 mmol). Yield 10.1 g (quant). 1H NMR: δH (CDCl3; 300 MHz): 1.24–1.52 (12 H,
m, CH2), 1.80 (2 H, m, O-CH2-CH2), 2.04 (2 H, m, CH2=CH-CH2), 3.87 (3 H, s, OCH3), 4.00 (2 H, t,
3J = 6.5 Hz, O-CH2), 4.95 (2 H, m, CH2=CH), 5.82 (1 H, m, CH2=CH), 6.90 (2 H, d, 3J = 9.0 Hz, Ar-
H), 7.97 (2 H, d, 3J = 9.0 Hz, Ar-H). 13C NMR: δC (CDCl3; 75 MHz): 26.4, 29.3, 29.5, 29.7, 29.8, 29.9,
34.2, 52.2, 68.6, 114.45, 114.5, 122.7, 131.9, 139.6, 163.4, 167.3.
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Supplementary material (ESI) for Journal of Materials Chemistry
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4-(10-Bromodecyloxy)benzaldehyde (5). Synthesized as described above for compound 1. Quantities:
K2CO3 (4.75 g, 34 mmol), p-hydroxybenzaldehyde (3.57 g, 29 mmol), 1,10-dibromodecane (8.6 mL,
38 mmol). Yield 10.0 g (quant.). 1H NMR: δH (CDCl3; 300 MHz): 1.22–1.52 (12 H, m, CH2), 1.80 (4
3
3
H, m, O-CH2-CH2 / Br-CH2-CH2), 3.36 (2 H, t, J = 6.9 Hz, Br-CH2), 4.00 (2 H, t, J = 6.5 Hz, O-
CH2), 6.95 (2 H, d, J = 8.7 Hz, Ar-H), 7.79 (2 H, d, J = 8.8 Hz, Ar-H), 9.84 (1 H, s, COH). 13C
NMR: δC (CDCl3; 75 MHz): 25.9, 28.1, 28.7, 29.0, 29.3, 29.4, 29.5, 32.8, 34.0, 68.4, 114.7, 129.7,
131.9, 164.2, 190.7.
3
3
4-(12-Bromododecyloxy)benzaldehyde (6). Synthesized as described above for compound 1.
Quantities: K2CO3 (4.6 g, 33 mmol), p-hydroxybenzaldehye (3.27 g, 27 mmol), 1,10-dibromododecane
(11.56 g, 35 mmol). Yield 7.0 g (70 %). 1H NMR: δH (CDCl3; 300 MHz): 1.24–1.52 (16 H, m, CH2),
1.84 (4 H, m, O-CH2-CH2 / Br-CH2-CH2), 3.40 (2 H, t, 3J = 6.9 Hz, Br-CH2), 4.06 (2 H, t, 3J = 6.5 Hz,
3
3
13
O-CH2), 6.98 (2 H, d, J = 8.7 Hz, Ar-H), 7.82 (2 H, d, J = 8.8 Hz, Ar-H), 9.88 (1 H, s, COH). C
NMR: δC (CDCl3; 75 MHz): 26.3, 28.6, 29.1, 29.4, 29.7, 29.8, 29.9, 33.2, 34.4, 68.8, 115.1, 130.1,
132.3, 164.6, 191.1.
4-(10-Bromodecyloxy)benzoic acid (7). Resorcinol (4.16 g, 38 mmol) and 5 (10.0 g, 29 mmol) were
dissolved in t-butanol (600 mL) through gentle heating to 70 °C. The solution was cooled to room
temperature, and a solution of NaH2PO4·H2O (13.7 g, 88 mmol) and NaClO2 (15.3 g, 170 mmol) in
deionized H2O (100 mL) was added dropwise to the flask over a period of 10 minutes. The purple-red
mixture was stirred overnight, following which it faded to a pale yellow colour. Volatile components
were removed, and the residue was taken in hexane (200 mL) and 1 M HCl (200 mL). The white
precipitate was filtered and washed profusely with distilled H2O and hexane. Yield 10.5 g (quant.). 1H
NMR: δH (CDCl3; 300 MHz): 1.26–1.55 (12 H, m, CH2), 1.86 (4 H, m, O-CH2-CH2 / Br-CH2-CH2),
3.44 (2 H, t, 3J = 6.8 Hz, Br-CH2), 4.04 (2 H, t, 3J = 6.5 Hz, O-CH2), 6.95 (2 H, d, 3J = 8.9 Hz, Ar-H),
3
13
8.07 (2 H, d, J = 8.9 Hz, Ar-H). C NMR: δC (CDCl3; 75 MHz): 26.0, 28.1, 28.7, 29.0, 29.3, 29.4,
32.8, 34.0, 68.3, 114.2, 121.4, 132.3, 163.7, 171.5.
4-(10-(Ethoxycarbonothioylthio)decyloxy)benzoic acid (8). Compound 7 (2.49 g, 7 mmol) was
dissolved in 600 mL of acetone that had been dried overnight over activated molecular sieves (4Å),
potassium o-ethyl xanthogenate (3.53 g, 22 mmol) was added to the flask, and the mixture was let to
stir for 3 days in the dark at 4 °C. The solvent was evaporated, and the residue was taken in CH2Cl2
(300 mL) and washed with 1 M HCl (50 mL). The product was then selectively precipitated from
1
dichloromethane through dropwise addition of petroleum ether. Yield 2.79 g (quant.). H NMR: δH
(CDCl3; 300 MHz): 1.24–1.52 (15 H, m, CH2 / O-CH2-CH3), 1.69 (2 H, m, S-CH2-CH2), 1.81 (2 H, m,
O-CH2-CH2), 3.11 (2 H, t, 3J = 7.3 Hz, SCH2), 4.02 (2 H, t, 3J = 6.5 Hz, O-CH2), 4.65 (2 H, q, 3J = 7.1
Hz, O-CH2-CH3), 6.93 (2 H, d, 3J = 8.8 Hz, Ar-H), 8.04 (2 H, d, 3J = 8.7 Hz, Ar-H).
4-(12-Bromododecyloxy)benzoic acid (9). Synthesized as described above for compound 7.
Quantities: resorcinol (2.69 g, 24 mmol), 6 (7.0 g, 19 mmol), NaH2PO4·H2O (8.87 g, 57 mmol),
NaClO2 (9.92 g, 110 mmol). Yield 7.32 g (quant.). 1H NMR: δH (CDCl3; 300 MHz): 1.24–1.52 (16 H,
m, CH2), 1.84 (4 H, m, O-CH2-CH2 / Br-CH2-CH2), 3.40 (2 H, t, 3J = 6.9 Hz, Br-CH2), 4.06 (2 H, t, 3J
3
3
13
= 6.5 Hz, O-CH2), 6.93 (2 H, d, J = 9.0 Hz, Ar-H), 8.04 (2 H, d, J = 8.9 Hz, Ar-H). C NMR: δC
(CDCl3; 75 MHz): 26.0, 28.2, 28.7, 29.1, 29.3, 29.4, 29.5, 32.8, 34.0, 68.3, 114.2, 121.3, 132.3, 163.7,
171.4.
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4-Formylphenyl 4-(decyloxy)benzoate (10). KOH (3.78 g, 67.6 mmol) was added to a solution of 1
(12.0 g, 41.0 mmol) dissolved in 250 mL of hot EtOH, and the mixture was refluxed for 24 hours. The
solvent was filtered off, and following drying over P2O5 the white solid was suspended in 300 mL of
toluene, and refluxed with oxalyl chloride (13.4 mL, 158.54) for 6 hours. Volatile components were
removed, the yellow solid was taken in CH2Cl2 (100 mL), and added to a stirred solution containing p-
hydroxybenzaldehyde (5.26 g, 43.1), triethylamine (36 mL, 0.261 mol), and DMAP (0.28 g, 2.3 mmol)
in CH2Cl2 (100 mL). The mixture was let to stir at room temperature for three hours, and then heated to
reflux for twelve hours. Following cooling to room temperature, the organic layer was washed with 1
M HCl (2 x 100 mL), and then distilled water (100 mL). The solvent was removed, and the product was
obtained as an off-white solid following recrystallization from ethanol. Yield (8.5 g, 54 %). 1H NMR:
3
δH (CDCl3; 300 MHz): 0.91 (3 H, t, J = 6.8 Hz, CH3), 1.21–1.58 (14 H, m, CH2), 1.85 (2 H, m, O-
3
CH2-CH2), 4.07 (2 H, t, 3J = 6.5 Hz, O-CH2), 7.00 (2 H, d, J = 9.0 Hz, Ar-H), 7.42 (2 H, d, 3J = 8.5
Hz, Ar-H), 7.98 (2 H, d, 3J = 8.6 Hz, Ar-H), 8.16 (2 H, d, 3J = 9.0 Hz, Ar-H), 10.03 (1 H, s, COH). 13C
NMR: δC (CDCl3; 75 MHz): 14.5, 23.1, 26.4, 29.5, 29.7, 29.8, 30.0, 32.3, 68.8, 114.8, 121.2, 123.0,
131.6, 132.8, 134.3, 156.3, 164.3, 164.6, 191.4.
4-Formylphenyl 4-(dodecyloxy)benzoate (11). Synthesized as described above for compound 10.
Quantities: 2 (9.58 g, 30 mmol), KOH (2.34, 42 mmol), oxalyl chloride (12 mL, 140 mmol), p-
hydroxybenzaldehyde (4.38 g, 36 mmol), triethylamine (32 mL, 0.23 mol), DMAP (0.19 g, 1.6 mmol).
1
3
Yield 11.6 g (97 %). H NMR: δH (CDCl3; 300 MHz): 0.89 (3 H, t, J = 6.9 Hz, CH3), 1.21–1.51 (18
H, m, CH2), 1.83 (2 H, m, O-CH2-CH2), 4.05 (2 H, t, 3J = 6.6 Hz, O-CH2), 6.99 (2 H, d, 3J = 9.0 Hz,
Ar-H), 7.40 (2 H, d, 3J = 8.5 Hz, Ar-H), 7.97 (2 H, d, 3J = 8.6 Hz, Ar-H), 8.16 (2 H, d, 3J = 9.0 Hz, Ar-
H), 10.0 (1 H, s, COH). 13C NMR: δC (CDCl3; 75 MHz): 14.5, 23.1, 26.4, 29.5, 29.6, 29.7, 32.2, 68.8,
114.8, 121.2, 123.0, 131.6, 132.8, 134.3, 156.3, 164.3, 164.6, 191.4.
4-Formylphenyl 4-(dec-9-enyloxy)benzoate (12). Synthesized as described above for compound 10.
Quantities: 3 (12.0 g, 41.3 mmol), KOH (3.62 g, 64.7 mmol), oxalyl chloride (12 mL, 0.15 mol), p-
hydroxybenzaldehyde (5.25 g, 43.0 mmol), triethylamine (35 mL, 0.25 mol), DMAP (0.25 g, 2.0
mmol). Yield 5.6 g (36 %). 1H NMR: δH (CDCl3; 300 MHz): 1.27–1.57 (10 H, m, CH2), 1.85 (2 H, m,
3
O-CH2-CH2), 2.07 (2 H, m, CH2=CH-CH2), 4.07 (2 H, t, J = 6.6 Hz, O-CH2), 4.99 (2 H, m,
CH2=CH), 5.84 (1 H, m, CH2=CH), 7.00 (2 H, d, 3J = 9.0 Hz, Ar-H), 7.42 (2 H, d, 3J = 8.5 Hz, Ar-H),
7.98 (2 H, d, 3J = 8.6 Hz, Ar-H), 8.16 (2 H, d, 3J = 9.0 Hz, Ar-H), 10.03 (1 H, s, COH). 13C NMR: δC
(CDCl3; 75 MHz): 26.4, 29.3, 29.4, 29.5, 29.7, 29.8, 34.2, 68.8, 114.6, 114.8, 121.2, 123.0, 131.6,
132.8, 134.3, 139.5, 156.3, 164.3, 164.6, 191.4.
4-Formylphenyl 4-(undec-10-enyloxy)benzoate (13). Synthesized as described above for compound
10. Quantities: 4 (10.10 g, 33 mmol), KOH (2.46, 45 mmol), oxalyl chloride (13 mL, 148 mmol), p-
hydroxybenzaldehyde (4.6 g, 38 mmol), triethylamine (33.7 mL, 0.24 mol), DMAP (0.20 g, 1.6 mmol).
Yield 8.9 g (71 %). 1H NMR: δH (CDCl3; 300 MHz): 1.24–1.52 (12 H, m, CH2), 1.83 (2 H, m, O-CH2-
CH2), 2.04 (2 H, m, CH2=CH-CH2), 4.05 (2 H, t, 3J = 6.5 Hz, O-CH2), 4.95 (2 H, m, CH2=CH), 5.82 (1
H, m, CH2=CH), 6.99 (2 H, d, 3J = 9.0 Hz, Ar-H), 7.40 (2 H, d, 3J = 8.5 Hz, Ar-H), 7.96 (2 H, d, 3J =
8.6 Hz, Ar-H), 8.14 (2 H, d, 3J = 9.0 Hz, Ar-H), 10.0 (1 H, s, COH). 13C NMR: δC (CDCl3; 75 MHz):
26.4, 29.3, 29.5, 29.5, 29.7, 29.8, 29.9, 34.2, 68.8, 114.6, 114.8, 121.2, 123.0, 131.6, 132.8, 134.3,
139.6, 156.3, 164.3, 164.6, 191.4.
4-Formylphenyl 4-(10-(ethoxycarbonothioylthio)decyloxy)benzoate (14).
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p-Hydroxybenzaldehyde (0.37 g, 3.0 mmol), 8 (1.2 g, 3.0 mmol), and DMAP (0.04 g, 0.3 mmol) were
dissolved in 300 mL of CH2Cl2. DCC (1.24 g, 6.0 mmol) was added to reaction flask which was stirred
at room temperature for three days. The solvent was removed under reduced pressure, and the residue
purified using column chromatography (CH2Cl2:EtOH, 10:0.05). The product was then recrystallized
from ethanol. Yield 0.3 g (20 %). 1H NMR: δH (CDCl3; 300 MHz): 1.24–1.52 (15 H, m, CH2 / O-CH2-
CH3), 1.69 (2 H, m, S-CH2-CH2), 1.81 (2 H, m, O-CH2-CH2), 3.11 (2 H, t, 3J = 7.3 Hz, SCH2), 4.02 (2
3
3
3
H, t, J = 6.5 Hz, O-CH2), 4.65 (2 H, q, J = 7.1 Hz, O-CH2-CH3), 6.99 (2 H, d, J = 8.9 Hz, Ar-H),
7.40 (2 H, d, 3J = 8.5 Hz, Ar-H), 7.96 (2 H, d, 3J = 8.6 Hz, Ar-H), 8.14 (2 H, d, 3J = 8.9 Hz, Ar-H), 10.0
(1 H, s, COH). C NMR: δC (CDCl3; 75 MHz): 13.8, 25.9, 28.1, 28.3, 28.8, 29.1, 29.3, 29.4, 35.9,
13
68.4, 69.7, 114.4, 120.8, 122.6, 131.2, 132.4, 133.9, 155.9.
4-Formylphenyl-4-(12-bromododecyloxy)benzoate (15). Synthesized as described for the preparation
of compound 14. Quantities: p-hydroxybenzaldehyde (1.78 g, 15 mmol), 9 (5.5 g, 14 mmol), DMAP
1
(0.25 g, 2.0 mmol), DCC (6.54 g, 32 mmol). Yield 5.2 g (79 %). H NMR: δH (CDCl3; 300 MHz):
3
1.24–1.52 (12 H, m, CH2), 1.84 (4 H, m, O-CH2-CH2 / Br-CH2-CH2), 3.40 (2 H, t, J = 6.9 Hz, Br-
CH2), 4.06 (2 H, t, 3J = 6.5 Hz, O-CH2), 6.99 (2H, d, 3J = 8.9 Hz, Ar-H), 7.40 (2 H, d, 3J = 8.5 Hz, Ar-
H), 7.97 (2 H, d, 3J = 8.6 Hz, Ar-H), 8.14 (2 H, d, 3J = 8.9 Hz, Ar-H), 10.00 (1 H, s, COH). 13C NMR:
δC (CDCl3; 75 MHz): 13.8, 25.9, 28.1, 28.3, 28.8, 29.1, 29.3, 29.3, 29.4, 35.9, 68.4, 69.7, 114.4, 120.8,
122.6, 131.2, 132.4, 133.9, 155.9.
4-(4-(Decyloxy)benzoyloxy)benzoic acid (16). Synthesized as described above for compound 7.
Quantities: resorcinol (3.18 g, 28.9 mmol), 10 (8.5 g, 22 mmol), NaH2PO4·H2O (10.39 g, 66.6 mmol),
1
3
NaClO2 (11.65 g, 0.13 mol). Yield 8.8 g (quant.). H NMR: δH (CDCl3; 300 MHz): 0.91 (3 H, t, J =
6.8 Hz, CH3), 1.23–1.59 (14 H, m, CH2), 1.85 (2 H, m, O-CH2-CH2), 4.07 (2 H, t, 3J = 6.5 Hz, O-CH2),
7.00 (2 H, d, 3J = 8.9 Hz, Ar-H), 7.36 (2 H, d, 3J = 8.6 Hz, Ar-H), 8.17 (2 H, d, 3J = 8.9 Hz, Ar-H), 8.22
3
13
(2 H, d, J = 8.6 Hz, Ar-H). C NMR: δC (CDCl3; 75 MHz): 14.5, 23.1, 26.4, 29.5, 29.7, 29.8, 30.0,
32.3, 68.8, 114.8, 121.4, 122.4, 127.0, 132.3, 132.8, 156.0, 164.2, 164.7, 171.7.
4-(4-(Dodecyloxy)benzoyloxy)benzoic acid (17). Synthesized as described above for compound 7.
Quantities: resorcinol (1.79 g, 16 mmol), 11 (5.52 g, 13 mmol), NaH2PO4·H2O (6.29 g, 40 mmol),
3
NaClO2 (7.03 g, 77 mmol). Yield 5.55 g (quant.). 1H NMR: δH (CDCl3; 300 MHz): 0.89 (3 H, t, J =
6.9 Hz, CH3), 1.17–1.71 (18 H, m, CH2), 1.83 (2 H, m, O-CH2-CH2), 4.05 (2 H, t, 3J = 6.6 Hz, O-CH2),
6.99 (2 H, d, 3J = 8.9 Hz, Ar-H), 7.35 (2 H, d, 3J = 8.6 Hz, Ar-H), 8.14 (2 H, d, 3J = 8.9 Hz, Ar-H), 8.17
(2 H, d, 3J = 8.6 Hz, Ar-H). 13C NMR: δC (CDCl3; 300 MHz): 14.1, 22.7, 26.0, 29.1, 29.3, 29.5, 29.6,
29.6, 29.7, 31.9, 68.4, 114.4, 120.9, 122.0, 126.5, 131.9, 132.4, 155.5, 170.3.
4-(4-(Dec-9-enyloxy)benzoyloxy)benzoic acid (18). Synthesized as described above for compound 7.
Quantities: resorcinol (2.11 g, 19.1 mmol), 12 (5.6 g, 14.7 mmol), NaH2PO4·H2O (6.89 g, 44.2 mmol),
1
NaClO2 (7.72 g, 85.4 mmol). Yield 5.8 g (quant). H NMR: δH (CDCl3; 300 MHz): 1.27–1.57 (10 H,
m, CH2), 1.85 (2 H, m, O-CH2-CH2), 2.08 (2 H, m, CH2=CH-CH2), 4.07 (2 H, t, 3J = 6.6 Hz, O-CH2),
4.99 (2 H, m, CH2=CH), 5.84 (1 H, m, CH2=CH), 7.00 (2 H, d, 3J = 8.9 Hz, Ar-H), 7.36 (2 H, d, 3J =
3
3
8.6 Hz, Ar-H), 8.17 (2 H, d, J = 8.9 Hz, Ar-H), 8.22 (2 H, d, J = 8.6 Hz, Ar-H). 13C NMR: δC
(CDCl3; 75 MHz): 26.4, 29.3, 29.4, 29.5, 29.7, 29.8, 34.2, 68.7, 114.6, 114.8, 121.34, 122.4, 127.0,
132.8, 139.5, 156.0, 164.2, 164.7, 171.7.
4-(4-(Undec-10-enyloxy)benzoyloxy)benzoic acid (19). Synthesized as described above for
compound 7. Quantities: resorcinol (1.71 g, 16 mmol), 13 (5.07 g, 13 mmol), NaH2PO4·H2O (5.32 g,
1
39 mmol), NaClO2 (6.71 g, 74 mmol). Yield 5.34 g (quant.). H NMR: δH (CDCl3; 300 MHz): 1.24–
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Supplementary material (ESI) for Journal of Materials Chemistry
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3
1.52 (12 H, m, CH2), 1.83 (2 H, m, O-CH2-CH2), 2.04 (2 H, m, CH2=CH-CH2), 4.05 (2 H, t, J = 6.5
Hz, O-CH2), 4.95 (2 H, m, CH2=CH), 5.82 (1 H, m, CH2=CH), 6.99 (2 H, d, 3J = 8.9 Hz, Ar-H), 7.34 (2
H, d, 3J = 8.6 Hz, Ar-H), 8.16 (2 H, d, 3J = 8.9 Hz, Ar-H), 8.20 (2 H, d, 3J = 8.6 Hz, Ar-H). 13C NMR:
δC (CDCl3; 75 MHz): 26.0, 28.9, 29.1, 29.3, 29.4, 29.5, 33.8, 68.4, 114.1, 114.4, 121.0, 122.0, 126.5,
131.9, 132.4, 139.2, 155.5, 163.8, 170.6.
4-(4-(10-(Ethoxycarbonothioylthio)decyloxy)benzoyloxy)benzoic acid (20). Synthesized as
described above for compound 7. Quantities: resorcinol (0.09 g, 0.78 mmol), 14 (0.30 g, 0.6 mmol),
1
NaH2PO4·H2O (0.28 g, 1.8 mmol), NaClO2 (0.31 g, 3.5 mmol). Yield 0.31 g (quant.). H NMR: δH
(CD3OD; 300 MHz): 1.24–1.73 (15 H, m, CH2 3/ O-CH2-CH3), 1.83 (4 H, m, S-CH2-CH2 / O-CH2-CH2),
2.80 (2 H, t, 3J = 7.3 Hz, SCH2), 4.11 (2 H, t, J = 6.2 Hz, OCH2), 4.85 (overlapping with solvent, O-
3
CH2-CH3), 7.08 (2 H, d, 3J = 8.9 Hz, Ar-H), 7.35 (2 H, d, J = 8.5 Hz, Ar-H), 8.13 (4H, m, Ar-H).
4-(4-(12-Bromododecyloxy))benzoyloxy)benzoic acid (21). Synthesized as described above for
compound 7. Quantities: resorcinol (0.73 g, 6.6 mmol), 15 (2.50 g, 5.1 mmol), NaH2PO4·H2O (2.39 g,
15 mmol), NaClO2 (2.67 g, 30 mmol). Yield 2.58 g (quant.). 1H NMR: δH (CDCl3; 300 MHz): 1.24–
1.52 (16 H, m, CH2), 1.84 (4 H, m, O-CH2-CH2 / Br-CH2-CH2), 3.40 (2 H, t, 3J = 6.9 Hz, Br-CH2), 4.06
(2 H, t, 3J = 6.5 Hz, O-CH2), 6.99 (2 H, d, 3J = 8.9 Hz, Ar-H), 7.30 (2 H, d, 3J = 8.6 Hz, Ar-H), 8.16 (2
H, d, 3J = 8.9 Hz, Ar-H), 8.20 (2 H, d, 3J = 8.6 Hz, Ar-H). 13C NMR: δC (CDCl3; 75 MHz): 26.0, 28.2,
28.7, 29.1, 29.3, 29.4, 29.5, 30.9, 32.8, 34.0, 68.4, 114.4, 121.0, 122.0, 126.6, 131.8, 132.4, 155.4,
163.8, 164.3, 169.8.
4-(4-(12-(Ethoxycarbonothioylthio)dodecyloxy)benzoyloxy)benzoic acid (22). Synthesized as
described above for compound 8. Quantities: potassium o-ethyl xanthogenate (5.0 g, 31.2 mmol), 21
(0.30 g, 0.6 mmol). Yield 0.3 g (quant.). 1H NMR: δH (CDCl3; 300 MHz): 1.23–1.57 (15 H, m, CH2 /
O-CH2-CH3), 1.71 (2 H, m, S-CH2-CH2), 1.85 (2 H, m, O-CH2-CH2), 3.14 (2 H, t, 3J = 7.5 Hz, SCH2),
4.07 (2 H, t, 3J = 6.2 Hz, OCH2), 4.67 (2 H, q, 3J = 7.1 Hz, O-CH2-CH3), 7.00 (2 H, d, 3J = 8.8 Hz, Ar-
H), 7.36 (2 H, d, 3J = 8.6 Hz, Ar-H), 8.16 (2 H, d, 3J = 8.8 Hz, Ar-H), 8.22 (2 H, d, 3J = 8.6 Hz, Ar-H).
13C NMR: δC (CDCl3; 75 MHz): 14.2, 26.4, 28.8, 29.3, 29.5, 29.75, 29.85, 29.9, 30.0, 36.3, 68.8, 70.1,
114.8, 121.4, 122.4, 127.0, 132.3, 132.8, 156.0, 164.2, 164.7, 171.7.
4-((3-Hydroxyphenoxy)carbonyl)phenyl 4-(decyloxy)benzoate (23). Compound 16 (2.05 g, 5.2
mmol) was suspended in toluene (100 mL), and refluxed with oxalyl chloride (2.0 mL, 23.2 mmol) for
five hours. Volatile components were removed, and the white solid was taken in CH2Cl2 (50 mL) and
added dropwise while stirring to a solution containing resorcinol (1.23 g, 11.2 mmol), triethylamine
(5.4 mL, 39 mmol), and DMAP (0.06 g, 0.52 mmol). Following stirring at room temperature for 12
hours, the mixture was then refluxed for twenty four hours. The solvent was removed under reduced
pressure, and the residue purified by column chromatography (CH2Cl2:EtOH, 10:0.03, and then
1
CH2Cl2:EtOH, 10:0.3). The product was then recrystallized from ethanol. Yield (1.6 g, 64%). H
NMR: δH (CDCl3; 300 MHz): 0.92 (3 H, t, 3J = 6.9 Hz, CH3), 1.23 – 1.60 (14 H, m, CH2), 1.86 (2 H,
m, O-CH2-CH2), 4.07 (2 H, t, 3J = 6.5 Hz, O-CH2), 6.15 (1 H, bs, OH), 6.69 (2 H, m, Ar-H), 6.78 (1 H,
d, 3J = 8.3 Hz, Ar-H), 7.01 (2 H, d, 3J = 8.9 Hz, Ar-H), 7.25 (1 H, t, 3J = 8.5 Hz, Ar-H), 7.38 (2 H, d, 3J
= 8.8 Hz, Ar-H), 8.18 (2 H, d, 3J = 8.9 Hz, Ar-H), 8.27 (2 H, d, 3J = 8.8 Hz, Ar-H). 13C NMR: δC
(CDCl3; 75 MHz): 14.5, 23.1, 26.4, 29.5, 29.7, 29.8, 30.0, 32.3, 68.8, 109.8, 113.8, 113.9, 114.9, 121.2,
122.6, 127.2, 130.5, 132.3, 132.9, 152.0, 155.8, 157.4, 164.3, 165.0, 165.3.
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Supplementary material (ESI) for Journal of Materials Chemistry
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4-((3-Hydroxyphenoxy)carbonyl)phenyl 4-(dodecyloxy)benzoatebenzoate (24). Synthesized as
described for the preparation of compound 23. Quantities: 21 (2.9 g, 7 mmol), oxalyl chloride (2.3 mL,
27.6 mmol), resorcinol (2.3 g, 2.1 mol), triethylamine (7.4 mL, 53 mmol), DMAP (0.09 g, 0.7 mmol).
Yield 1.37 g (38 %). 1H NMR: δH (CDCl3; 300 MHz): 0.91 (3 H, t, 3J = 6.9 Hz, CH3), 1.23 – 1.56 (18
H, m, CH2), 1.85 (2 H, m, O-CH2-CH2), 4.08 (2 H, t, 3J = 6.6 Hz, O-CH2), 4.98 (1 H, bs, OH), 6.76 (2
3
3
3
H, m, Ar-H), 6.83 (1 H, d, J = 8.3 Hz, Ar-H), 7.01 (2 H, d, J = 9.0 Hz, Ar-H), 7.30 (1 H, t, J = 8.5
Hz, Ar-H), 7.39 (2 H, d, 3J = 8.8 Hz, Ar-H), 8.18 (2 H, d, 3J = 8.9 Hz, Ar-H), 8.29 (2 H, d, 3J = 8.8 Hz,
Ar-H). 13C NMR: δC (CDCl3; 75 MHz): 14.1, 22.7, 26.0, 29.1, 29.3, 29.55, 29.6, 29.65, 31.9, 53.4,
68.4, 109.3, 113.1, 114.0, 114.4, 120.9, 122.1, 126.8, 131.8, 132.4, 151.8, 155.4, 156.5, 163.8, 164.4.
4-((3-Hydroxyphenoxy)carbonyl)phenyl 4-(12-bromododecyloxy)benzoate (25). Synthesized as
described for the preparation of compound 23. Quantities: 21 (1.5 g, 3 mmol), oxalyl chloride (1.6 mL,
18.9 mmol), resorcinol (0.66 g, 6 mol), triethylamine (3 mL, 23 mmol), DMAP (0.04 g, 0.3 mmol).
1
Yield 0.7 g (36 %). H NMR: δH (CDCl3; 300 MHz): 1.27 – 1.58 (16 H, m, CH2), 1.86 (4 H, m, O-
CH2-CH2, Br-CH2-CH2), 3.43 (2 H, t, 3J = 6.8 Hz, Br-CH2), 4.07 (2 H, t, 3J = 6.5 Hz, O-CH2), 6.70 (2
3
3
3
H, m, Ar-H), 6.77 (1 H, d, J = 8.1 Hz, Ar-H), 7.00 (2 H, d, J = 8.8 Hz, Ar-H), 7.25 (1 H, t, J = 8.5
Hz, Ar-H), 7.37 (2 H, d, 3J = 8.7 Hz, Ar-H), 8.17 (2 H, d, 3J = 8.8 Hz, Ar-H), 8.27 (2 H, d, 3J = 8.7 Hz,
Ar-H). 13C NMR: δC (CDCl3; 75 MHz): 26.4, 28.6, 29.2, 29.5, 29.8, 29.8, 29.9, 33.2, 34.5, 68.8, 109.7,
113.8, 113.9, 114.9, 121.2, 122.5, 127.2, 130.5, 132.3, 132.9, 152.0, 155.8, 157.5, 164.3, 165.0, 165.2.
1.3 Bent-core Derivatives BC1-BC16
1,3-Phenylene bis(4-(4-(decyloxy)benzoyloxy)benzoate) (BC1). Resorcinol (0.3 g, 2.5 mmol), 14
(1.89 g, 4.7 mmol), and DMAP (0.6 g, 5.1 mmol) were dissolved in 50 mL of CH2Cl2. DCC (2.07 g,
10.0 mmol) was added to reaction flask which was stirred at room temperature for 48 hours. The
solvent was removed under reduced pressure, and the residue purified using column chromatography
(CH2Cl2:EtOH, 10:0.03). The product was then selectively precipitated from CH2Cl2 through dropwise
addition of petroleum ether. Yield 1.5 g (68 %). EA: Found: C, 74.36; H, 7.16. C54H62O10 requires C,
3
74.46; H, 7.17 %. 1H NMR: δH (CDCl3; 300 MHz): 0.94 (6 H, t, J = 6.7 Hz, CH3), 1.19–1.60 (28 H,
m, CH2), 1.85 (4 H, m, O-CH2-CH2), 4.06 (4 H, t, 3J = 6.4 Hz, O-CH2), 7.00 (4 H, d, 3J = 8.7 Hz, Ar-
H), 7.22 (3 H, m, Ar-H), 7.39 (4 H, d, 3J = 8.6 Hz, Ar-H), 7.50 (1 H, t, 3J = 8.1 Hz, Ar-H), 8.17 (4 H, d,
3J = 8.7 Hz, Ar-H), 8.28 (4 H, d, 3J = 8.6 Hz, Ar-H). 13C NMR: δC (CDCl3; 75 MHz): 14.6, 23.1, 26.4,
29.5, 29.8, 30.0, 32.3, 68.8, 114.8, 116.2, 119.7, 121.4, 122.5, 127.0, 130.2, 132.2, 132.8, 151.9, 155.9,
164.2, 164.4, 164.6. m/z (MALDI) 893.63 [M+Na]+, C54H62NaO10 requires 893.42.
1,3-Phenylene bis(4-(4-(dodecyloxy)benzoyloxy)benzoate) (BC2). Synthesized as described for the
preparation of compound BC1. Quantities: resorcinol (0.12 g, 1.1 mmol), 15 (0.97 g, 2.3 mmol),
DMAP (0.02 g, 0.1 mmol), DCC (0.91 g, 4.4 mmol). Yield 0.53 g (53 %). EA: Found: C, 74.98; H,
1
3
7.50. C58H70O10 requires C, 75.13; H, 7.61 %. H NMR: δH (CDCl3; 300 MHz): 0.89 (6 H, t, J = 6.9
3
Hz, CH3), 1.24–1.48 (36 H, m, CH2), 1.84 (4 H, m, O-CH2-CH2-), 4.06 (4 H, t, J = 6.5 Hz, O-CH2),
6.99 (4 H, d, 3J = 9.0 Hz, Ar-H), 7.19 (3 H, m, Ar-H), 7.38 (4 H, d, 3J = 8.8 Hz, Ar-H), 7.50 (1 H, t, 3J
3
3
13
= 8.3 Hz, Ar-H), 8.16 (4 H, d, J = 8.9 Hz, Ar-H), 8.28 (4 H, d, J = 8.8 Hz, Ar-H). C NMR: δC
(CDCl3; 75 MHz): 14.1, 22.7, 26.0, 29.1, 29.3, 29.5, 29.6, 29.7, 31.9, 68.4, 114.4, 115.8, 119.3, 120.9,
122.1, 126.6, 129.9, 131.9, 132.4, 151.4, 155.5, 163.8, 164.1, 164.3. m/z (MALDI) 950.06 [M+Na]+,
C58H70NaO10 requires 949.49.
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Supplementary material (ESI) for Journal of Materials Chemistry
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1,3-Phenylene bis(4-(4-(undec-10-enyloxy)benzoyloxy)benzoate) (BC3). Synthesized as described
for the preparation of compound BC1. Quantities: resorcinol (0.13 g, 1.1 mmol), 17 (0.92 g, 2.2 mmol),
DMAP (0.03 g, 0.2 mmol), DCC (0.92 g, 4.5 mmol). Yield 0.72 g (71 %). EA: Found: C, 74.88; H,
1
7.22. C56H62O10 requires C, 75.14; H, 6.98 %. H NMR: δH (CDCl3; 300 MHz): 1.24–1.43 (24 H, m,
3
CH2), 1.84 (4 H, m, O-CH2-CH2-), 2.04 (4 H, m, CH2-CH=CH2), 4.06 (4 H, t, J = 6.5 Hz, O-CH2),
4.95 (4 H, m, CH=CH2), 5.80 (2 H, m, CH=CH2), 6.99 (4 H, d, 3J = 8.9 Hz, Ar-H), 7.19 (3 H, m, Ar-
H), 7.38 (4 H, d, 3J = 8.7 Hz, Ar-H), 7.50 (1 H, t, 3J = 8.3 Hz, Ar-H), 8.16 (4 H, d, 3J = 8.9 Hz, Ar-H),
3
13
8.28 (4 H, d, J = 8.7 Hz, Ar-H). C NMR: δC (CDCl3; 75 MHz): 26.4, 29.3, 29.4, 29.5, 29.7, 29.8,
29.9, 34.2, 68.8, 114.5, 114.8, 116.2, 119.7, 121.4, 122.5, 127.0, 130.3, 132.3, 132.8, 139.6, 151.8,
155.9, 164.2, 164.5, 164.7. m/z (MALDI) 918.25 [M+Na]+, C56H62NaO10 requires 917.42.
1,3-Phenylene bis(4-(4-(11-(acetylthio)undecyloxy)benzoyloxy)benzoate) (BC4). Compound BC3
(0.81 g, 0.9 mmol), thioacetic acid (0.5 mL, 7.2 mmol), and AIBN (0.1 g, 0.6 mmol) were dissolved in
THF (50 mL), and the solution was irradiated with UV light while stirring for 3 hours. The solvent was
removed, and the residue purified by column chromatography (CH2Cl2:EtOH, 10:0.03). The product
was selectively precipitated from CH2Cl2 through dropwise addition of petroleum ether. Yield 0.9 g (93
%). EA: Found: C, 68.37; H, 7.00. C60H70NaO12S2 requires C, 68.81; H, 6.74 %. 1H NMR: δH (CDCl3;
300 MHz): 1.27–1.65 (32 H, m, CH2), 1.85 (4 H, m, O-CH2-CH2), 2.35 (6 H, s, COCH3), 2.89 (2 H, t,
3J = 7.3, SCH2), 4.06 (4 H, t, 3J = 6.5 Hz, OCH2), 6.99 (4 H, d, 3J = 9.0 Hz, Ar-H), 7.22 (3 H, m, Ar-
H), 7.40 (4 H, d, 3J = 8.8 Hz, Ar-H), 7.50 (1 H, t, 3J = 8.3 Hz, Ar-H), 8.17 (4 H, d, 3J = 8.9 Hz, Ar-H),
3
13
8.29 (4 H, d, J = 8.8 Hz, Ar-H). C NMR: δC (CDCl3; 75 MHz): 14.1, 22.7, 26.0, 28.8, 29.1, 29.35,
29.4, 29.5, 29.55, 29.6, 29.65, 29.7, 31.9, 68.4, 114.4, 115.8, 119.3, 120.9, 122.1, 126.6, 129.9, 131.8,
132.4, 151.4, 151.4, 155.5, 163.8, 164.1, 164.3, 196.0. m/z (MALDI) 1069.64 [M+Na]+,
C60H70NaO12S2 requires 1069.42.
1,3-Phenylene bis(4-(4-(11-mercaptoundecyloxy)benzoyloxy)benzoate) (BC5). Compound BC4
(0.2 g, 0.2 mmol) was dissolved in 50:50 THF/MeOH (20 mL), and following addition of 3 mL conc.
HCl to the flask, the mixture was heated to reflux for 6 hours. The mixture was let to cool to room
temperature, diluted with water (10 mL), and extracted with CH2Cl2 (2 x 200 mL). The solvent was
removed, and the residue purified by column chromatography (CH2Cl2:EtOH, 10:0.03). The product
was then selectively precipitated from CH2Cl2 through dropwise addition of petroleum ether. Yield
0.11 g (60 %). EA: Found: C, 69.37; H, 7.21. C56H66O10S2 requires C, 69.83; H, 6.91 %. 1H NMR: δH
(CDCl3; 300 MHz): 1.24–1.56 (30 H, m, CH2 / SH), 1.63 (4 H, m, S-CH2-CH2), 1.85 (4 H, m, O-CH2-
CH2), 2.55 (4 H, q, 3J = 7.4, SCH2), 4.07 (4 H, t, 3J = 6.5 Hz, OCH2), 7.01 (4 H, d, 3J = 8.9 Hz, Ar-H),
7.22 (3 H, m, Ar-H), 7.40 (4 H, d, 3J = 8.7 Hz, Ar-H), 7.50 (1 H, t, 3J = 8.2 Hz, Ar-H), 8.17 (4 H, d, 3J
3
13
= 8.9 Hz, Ar-H), 8.29 (4 H, d, J = 8.7 Hz, Ar-H). C NMR: δC (CDCl3; 75 MHz): 25.1, 26.4, 28.8,
29.5, 29.7, 29.9, 29.9, 34.4, 53.8, 68.8, 114.8, 116.2, 119.7, 121.4, 122.5, 127.0, 130.3, 132.3, 132.8,
151.8, 155.9, 164.2, 164.5, 164.7. m/z (MALDI) 985.81 [M+Na]+, C56H66NaO10S2 requires 985.40.
.
1,3-Phenylene bis(4-(4-(12-bromododecyloxy)benzoyloxy)benzoate)
(BC6). Synthesized as
described for the preparation of compound BC1. Quantities: resorcinol (0.12 g, 1.1 mmol), 12 (1.0 g,
2.0 mmol), DMAP (0.03 g, 0.2 mmol), DCC (0.95 g, 4.6 mmol). Yield 0.56 g (48 %). EA: Found: C,
1
64.60; H, 6.09. C58H68Br2O10 requires C, 64.21; H, 6.32 %. H NMR: δH (CDCl3; 300 MHz): 1.24–
1.52 (32 H, m, CH2), 1.84 (8 H, m, O-CH2-CH2 / Br-CH2-CH2), 3.40 (4 H, t, 3J = 6.9 Hz, Br-CH2), 4.06
(4 H, t, 3J = 6.5 Hz, O-CH2), 6.99 (4 H, d, 3J = 9.0 Hz, Ar-H), 7.19 (3 H, m, Ar-H), 7.38 (4 H, d, 3J =
8.8 Hz, Ar-H), 7.50 (1 H, t, 3J = 8.3 Hz, Ar-H), 8.16 (4 H, d, 3J = 8.9 Hz, Ar-H), 8.28 (4 H, d, 3J = 8.8
Hz, Ar-H). 13C NMR: δC (CDCl3; 75 MHz): 26.0, 28.2, 28.8, 29.1, 29.35, 29.4, 29.5, 32.8, 34.1, 68.4,
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Supplementary material (ESI) for Journal of Materials Chemistry
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114.4, 115.8, 119.3, 121.0, 122.2, 126.6, 129.9, 131.9, 132.4, 151.4, 155.5, 163.8, 164.1, 164.3. m/z
(MALDI) 1105.67 (100%) and 1107.67 (51%) [M+Na]+, C58H68Br2NaO10 requires 1105.31 (51%) and
1107.31 (100%).
1,3-Phenylene bis(4-(4-(12-(ethoxycarbonothioylthio)dodecyloxy)benzoyloxy) benzoate) (BC7).
Synthesized as described for the preparation of compound 8. Quantities: BC6 (0.10 g, 0.09 mmol),
potassium o-ethyl xanthogenate (0.04 g, 0.2 mmol). Yield 0.12 g (quant.). EA: Found: C, 65.16; H,
7.83. C64H78O12S4 requires C, 65.84; H, 6.73 %. 1H NMR: δH (CDCl3; 300 MHz): 1.24–1.56 (38 H, m,
3
CH2 / O-CH2-CH3), 1.71 (2 H, m, S-CH2-CH2), 1.85 (4 H, m, O-CH2-CH2), 3.11 (4 H, t, J = 7.4 Hz,
SCH2), 4.07 (4 H, t, 3J = 6.5 Hz, O-CH2), 4.67 (4 H, q, 3J = 7.1 Hz, O-CH2-CH3), 7.01 (2 H, d, 3J = 8.7
Hz, Ar-H), 7.21 (3 H, m, Ar-H), 7.40 (4 H, d, 3J = 8.5 Hz, Ar-H), 7.50 (1 H, t, 3J = 8.1 Hz, Ar-H), 8.17
13
(4 H, d, 3J = 8.7 Hz, Ar-H), 8.29 (4 H, d, 3J = 8.5 Hz, Ar-H). C NMR: δC (CDCl3; 75 MHz): 13.8,
26.0, 28.3, 28.9, 29.1, 29.3, 29.4, 29.5, 35.9, 68.4, 69.7, 114.4, 115.8, 119.3, 120.9, 122.1, 126.6, 129.9,
131.9, 132.4, 151.4, 155.5, 163.8, 164.1, 164.3, 171.6. m/z (MALDI) 1189.33 [M+Na]+,
C64H78NaO12S4 requires 1189.43.
4-((3-(4-(4-(Dec-9-enyloxy)benzoyloxy)benzoyloxy)phenoxy)carbonyl)phenyl
4-(decyloxy)-
benzoate (BC8). Synthesized as described for the preparation of compound BC1. Quantities: 23 (0.58
g, 1.2 mmol), 18 (0.51 g, 1.3 mmol), DMAP (0.19 g, 1.6 mmol), DCC (0.5 g, 2.4 mmol). Yield 0.68 g
(58 %). EA: Found: C, 74.69; H, 7.10. C54H60O10 requires C, 74.63; H, 6.96 %. 1H NMR: δH (CDCl3;
300 MHz): 0.93 (3 H, t, 3J = 6.7 Hz, CH3), 1.18–1.61 (24 H, m, CH2), 1.85 (4 H, m, O-CH2-CH2-), 2.09
3
(4 H, m, CH2-CH=CH2), 4.06 (4 H, t, J = 6.4 Hz, O-CH2), 5.01 (4 H, m, CH=CH2), 5.86 (2 H, m,
CH=CH2), 7.01 (4 H, d, 3J = 8.7 Hz, Ar-H), 7.23 (3 H, m, Ar-H), 7.40 (4 H, d, 3J = 8.6 Hz, Ar-H), 7.50
3
3
3
13
(1 H, t, J = 8.1 Hz, Ar-H), 8.18 (4 H, d, J = 8.7 Hz, Ar-H), 8.27 (4 H, d, J = 8.6 Hz, Ar-H). C
NMR: δC (CDCl3; 75 MHz): 14.2, 22.7, 26.0, 28.9, 29.1, 29.35, 29.4, 29.6, 68.4, 114.3, 114.5, 115.8,
119.3, 121.0, 122.2, 126.6, 129.9, 131.8, 132.4, 139.1, 151.5, 155.5, 163.8, 164.0, 164.2. m/z (MALDI)
891.43 [M+Na]+, C54H60NaO10 requires 891.41.
4-((3-(4-(4-(10-(Acetylthio)decyloxy)benzoyloxy)benzoyloxy)phenoxy)carbonyl) phenyl 4-(decyl-
oxy)benzoate (BC9). Synthesized as described for the preparation of compound BC4. Quantities: BC8
(0.55 g, 0.61 mmol), thioacetic acid (0.3 mL, 4.90 mmol), and AIBN (0.1 g, 0.61 mmol). Yield 0.5 g
(86 %). EA: Found: C, 70.85; H, 6.91. C56H64O11S requires C, 71.16; H, 6.82 %. 1H NMR: δH (CDCl3;
300 MHz): 0.91 (3 H, t, 3J = 6.9 Hz, CH3), 1.21–1.66 (28 H, m, CH2), 1.85 (4 H, m, O-CH2-CH2), 2.34
(3 H, s, COCH3), 2.89 (2 H, t, 3J = 7.3, SCH2), 4.07 (4 H, t, 3J = 6.5 Hz, OCH2), 7.01 (4 H, d, 3J = 8.9
Hz, Ar-H), 7.21 (3 H, m, Ar-H), 7.40 (4 H, d, 3J = 8.7 Hz, Ar-H), 7.52 (1 H, t, 3J = 8.1 Hz, Ar-H), 8.17
3
3
(4 H, d, J = 8.8 Hz, Ar-H), 8.30 (4 H, d, J = 8.7 Hz, Ar-H). 13C NMR: δC (CDCl3; 75 MHz):14.5,
23.1, 26.35, 26.4, 29.2, 29.45, 29.5, 29.7, 29.8, 29.85, 29.9, 30.0, 31.0, 32.3, 68.75, 68.8, 114.8, 116.2,
119.7, 121.3, 122.6, 127.0, 130.3, 132.3, 132.8, 151.8, 155.9, 164.2, 164.5, 164.7, 196.4. m/z (MALDI)
967.39 [M+Na]+, C56H64NaO11S requires 967.41.
4-((3-(4-(4-(Decyloxy)benzoyloxy)benzoyloxy)phenoxy)carbonyl)phenyl 4-(10-mercaptodecyloxy)
benzoate (BC10). Synthesized as described for the preparation of compound 27. Quantities: BC9 (0.45
g, 0.48 mmol), 12M HCl (2 mL). Yield 0.26 g (60 %). EA: Found: C, 71.44; H, 6.93. C54H62O10S
3
requires C, 71.82; H, 6.92 %. 1H NMR: δH (CDCl3; 300 MHz): 0.91 (3 H, t, J = 6.8 Hz, CH3), 1.17–
3
1.57 (27 H, m, CH2 / SH), 1.63 (2 H, m, S-CH2-CH2), 1.85 (4 H, m, O-CH2-CH2), 2.55 (2 H, q, J =
3
3
7.2, SCH2), 4.07 (4 H, t, J = 6.5 Hz, OCH2), 7.01 (4 H, d, J = 8.9 Hz, Ar-H), 7.21 (3 H, m, Ar-H),
7.40 (4 H, d, 3J = 8.7 Hz, Ar-H), 7.52 (1 H, t, 3J = 8.1 Hz, Ar-H), 8.18 (4 H, d, 3J = 8.8 Hz, Ar-H), 8.30
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(4 H, d, 3J = 8.7 Hz, Ar-H). 13C NMR: δC (CDCl3; 75 MHz): 14.5, 23.1, 25.1, 26.4, 28.8, 29.45, 29.5,
29.7, 29.75, 29.8, 29.9, 30.0, 32.3, 34.4, 68.75, 68.8, 114.8, 116.2, 119.7, 121.3, 121.4, 122.6, 127.0,
130.3, 132.3, 132.8, 151.8, 155.9, 163.8, 164.1, 164.3. m/z (MALDI) 941.36 [M+K]+, C54H62KO10S
requires 941.37.
4-((3-(4-(4-(12-Bromododecyloxy)benzoyloxy)benzoyloxy)phenoxy)carbonyl)phenyl 4-(dodecyl-
oxy)benzoate (BC11). Synthesized as described for the preparation of compound BC1. Quantities: 25
(0.15 g, 0.25 mmol), 17 (0.11 g, 0.25 mmol), DMAP (0.03 g, 0.25 mmol), DCC (0.10 g, 0.5 mmol).
1
Yield 0.18 g (72 %). EA: Found: C, 69.39; H, 7.13. C58H69BrO10 requires C, 69.24; H, 6.91 %. H
NMR: δH (CDCl3; 300 MHz): 0.91 (3 H, t, 3J = 6.8 Hz, CH3), 1.19–1.56 (34 H, m, CH2), 1.85 (6 H, m,
O-CH2-CH2 / Br-CH2-CH2), 3.43 (2 H, t, 3J = 6.8 Hz, CH2Br), 4.08 (4 H, t, 3J = 6.5 Hz, OCH2), 7.01 (2
H, d, 3J = 8.8 Hz, Ar-H), 7.21 (3 H, m, Ar-H), 7.40 (4 H, d, 3J = 8.6 Hz, Ar-H), 7.52 (1 H, t, 3J = 8.1
Hz, Ar-H), 8.18 (4 H, d, 3J = 8.8 Hz, Ar-H), 8.30 (4 H, d, 3J = 8.6 Hz, Ar-H). 13C NMR: δC (CDCl3; 75
MHz): 14.5, 23.1, 26.4, 28.6, 29.2, 29.5, 29.75, 29.8, 29.85, 29.9, 29.95, 30.0, 32.3, 33.2, 34.4, 68.8,
114.7, 114.8, 116.2, 119.7, 121.4, 122.5, 127.0, 130.2, 132.2, 132.25, 132.3, 132.8, 151.8, 151.85,
155.9, 164.2, 164.5, 164.7. m/z (MALDI) 1028.00 (100%) and 1030.03 (97%) [M+Na]+,
C58H69BrNaO10 requires 1027.40 (100%) and 1029.40 (97%).
4-((3-(4-(4-(12-Bromododecyloxy)benzoyloxy)benzoyloxy)phenoxy)carbonyl)phenyl
4-(12-
(ethoxycarbonothioylthio)dodecyloxy)benzoate (BC12). Synthesized as described for the preparation
of compound BC1. Quantities: 25 (0.22 g, 0.37 mmol), 22 (0.20 g, 0.37 mmol), DMAP (0.045 g, 0.37
mmol), DCC (0.15 g, 0.73 mmol). Yield 0.25 g (61 %). EA: Found: C, 64.49; H, 6.81. C61H73BrO11S2
1
requires C, 65.05; H, 6.53 %. H NMR: δH (CDCl3; 300 MHz): 1.22–1.62 (35 H, m, CH2 / O-CH2-
CH3), 1.71 (2 H, m, S-CH2-CH2), 1.87 (6 H, m, O-CH2-CH2 / Br-CH2-CH2), 3.13 (2 H, t, 3J = 7.4 Hz,
SCH2), 3.42 (2 H, t, 3J = 6.8 Hz, CH2Br), 4.07 (4 H, t, 3J = 6.5 Hz, OCH2), 4.66 (2 H, q, 3J = 7.1 Hz, O-
3
3
CH2-CH3), 7.01 (2 H, d, J = 8.7 Hz, Ar-H), 7.21 (3 H, m, Ar-H), 7.40 (4 H, d, J = 8.5 Hz, Ar-H),
7.51 (1 H, t, 3J = 8.1 Hz, Ar-H), 8.17 (4 H, d, 3J = 8.7 Hz, Ar-H), 8.30 (4 H, d, 3J = 8.5 Hz, Ar-H). 13C
NMR: δC (CDCl3; 75 MHz): 13.8, 26.0, 28.2, 28.3, 28.8, 28.9, 29.0, 29.3, 29.35, 29.4, 29.5, 31.7, 32.8,
34.0, 35.9, 53.8, 68.4, 69.5, 69.7, 114.4, 115.8, 119.3, 120.9, 122.1, 126.6, 129.9, 131.9, 132.4, 151.4,
155.5, 163.8, 164.1, 164.3, 210.8. m/z (MALDI) 1147.56 (100%) and 1149.59 (97%) [M+Na]+,
C61H73BrNaO11S2 requires 1147.37 (100.0%) and 1149.37 (97%).
4-((3-(4-(4-(Dodecyloxy)benzoyloxy)benzoyloxy)phenoxy)carbonyl)phenyl 4-(undec-10-enyloxy)
benzoate (BC13). Synthesized as described for the preparation of compound BC1. Quantities: 24 (1.08
g, 2.64 mmol), 18 (1.37 g, 2.64 mmol), DMAP (0.32 g, 2.64 mmol), DCC (0.32 g, 5.28 mmol). Yield
1
1.5 g (62 %). EA: Found: C, 74.91; H, 7.30. C57H66O10 requires C, 75.14; H, 7.30 %. H NMR: δH
3
(CDCl3; 300 MHz): 0.89 (3 H, t, J = 6.9 Hz, CH3), 1.24–1.43 (30 H, m, CH2), 1.84 (4 H, m, O-CH2-
3
CH2-), 2.04 (2 H, m, CH2-CH=CH2), 4.06 (4 H, t, J = 6.5 Hz, O-CH2), 4.95 (2 H, m, CH=CH2), 5.80
3
(1 H, m, CH=CH2), 6.99 (4 H, d, J = 8.9 Hz, Ar-H), 7.19 (3 H, m, 3H, Ar-H), 7.38 (4 H, d, 3J = 8.7
Hz, Ar-H), 7.50 (1 H, t, 3J = 8.1 Hz, Ar-H), 8.16 (4 H, d, 3J = 8.9 Hz, Ar-H), 8.28 (4 H, d, 3J = 8.7 Hz,
Ar-H). 13C NMR: δC (CDCl3; 75 MHz): 14.2, 22.7, 26.0, 28.9, 29.1, 29.4, 29.45, 29.5, 29.6, 29.65,
29.7, 31.9, 33.8, 68.4, 114.2, 114.4, 115.8, 119.3, 121.0, 122.1, 126.6, 129.7, 131.8, 132.4, 139.1,
151.5, 155.5, 163.8, 164.0, 164.2. m/z (MALDI) 934.16 [M+Na]+, C57H66NaO10 requires 933.46.
4-((3-(4-(4-(11-(Acetylthio)undecyloxy)benzoyloxy)benzoyloxy)phenoxy)carbonyl)
phenyl
4-
(dodecyloxy)benzoate (BC14). Synthesized as described for the preparation of compound BC4.
Quantities: BC13 (0.30 g, 0.3 mmol), thioacetic acid (0.2 mL, 2.6 mmol), AIBN (0.05 g, 0.3 mmol).
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Yield 0.25 g (84 %). EA: Found: C, 71.44; H, 6.93. C59H70O11S requires C, 71.78; H, 7.15 %. H
NMR: δH (CDCl3; 300 MHz): 0.91 (3 H, t, 3J = 6.9 Hz, CH3), 1.21–1.66 (36 H, m, CH2), 1.84 (4 H, m,
3
3
O-CH2-CH2), 2.33 (3 H, s, COCH3), 2.89 (2 H, t, J = 7.3, SCH2), 4.06 (4 H, t, J = 6.5 Hz, OCH2),
6.99 (4 H, d, 3J = 8.9 Hz, Ar-H), 7.22 (3 H, m, Ar-H), 7.40 (4 H, d, 3J = 8.7 Hz, Ar-H), 7.50 (1 H, t, 3J
3
3
13
= 8.1 Hz, Ar-H), 8.17 (4 H, d, J = 8.8 Hz, Ar-H), 8.29 (4 H, d, J = 8.7 Hz, Ar-H). C NMR: δC
(CDCl3; 75 MHz): 14.5, 14.55, 22.7, 23.1, 26.4, 29.2, 29.5, 29.6, 29.7, 29.75, 29.8, 29.9, 30.0, 30.1,
31.0, 32.3, 68.8, 114.8, 116.2, 119.7, 121.3, 122.5, 127.0, 130.3, 132.2, 132.8, 151.8, 155.9, 164.2,
164.5, 164.7, 196.4. m/z (MALDI) 1009.98 [M+Na]+, C59H70NaO11S 1009.45.
4-((3-(4-(4-(Dodecyloxy)benzoyloxy)benzoyloxy)phenoxy)carbonyl)phenyl
4-(11-mercaptoun-
decyloxy)benzoate (BC15). Synthesized as described for the preparation of compound BC5.
Quantities: BC14 (0.16 g, 0.2 mmol), 12 M HCl (2 mL). Yield 0.10 g (67 %). EA: Found: C, 72.25; H,
7.50. C57H68O10S requires C, 72.43; H, 7.25 %. 1H NMR: δH (CDCl3; 300 MHz): 0.91 (3 H, t, 3J = 6.9
3
Hz, CH3), 1.19–1.70 (37 H, m, CH2 / SH), 1.85 (4 H, m, O-CH2-CH2), 2.55 (2 H, q, J = 7.3 Hz,
SCH2), 4.06 (4 H, t, 3J = 6.5 Hz, OCH2), 7.01 (4 H, d, 3J = 8.7 Hz, Ar-H), 7.22 (3 H, m, Ar-H), 7.40 (4
H, d, 3J = 8.6 Hz, Ar-H), 7.50 (1 H, t, 3J = 8.0 Hz, Ar-H), 8.17 (4 H, d, 3J = 8.7 Hz, Ar-H), 8.29 (4 H, d,
3J = 8.5 Hz, Ar-H). 13C NMR: δC (CDCl3; 75 MHz): 14.6, 23.1, 25.1, 26.4, 28.8, 29.5, 29.7, 29.9,
29.95, 30.0, 30.05, 30.1, 32.3, 34.4, 68.8, 114.8, 116.2, 119.7, 121.3, 122.2, 122.5, 127.0, 130.3, 132.3,
132.75, 132.8, 151.8, 155.9, 164.2, 164.5, 164.7. m/z (MALDI) 967.93 [M+Na]+, C57H68NaO10S
requires 967.44.
4-((3-(4-(4-(Dodecyloxy)benzoyloxy)benzoyloxy)phenoxy)carbonyl)phenyl 4-(10-(ethoxycarbono-
thioylthio)decyloxy)benzoate (BC16). Synthesized as described for the preparation of compound
BC1. Quantities: 20 (0.21 g, 0.4 mmol), 24 (0.18 g, 0.4 mmol), DMAP (0.01 g, 0.09 mmol), DCC
(1.12 g, 5.4 mmol). Yield 0.15 g (37 %). EA: Found: C, 69.52; H, 7.05. C61H74O11S2 requires C, 69.52;
H, 6.92 %. 1H NMR: δH (CDCl3; 300 MHz): 0.91 (3 H, t, 3J = 6.9 Hz, CH3), 1.24–1.57 (33 H, m, CH2 /
O-CH2-CH3), 1.67 (2 H, m, S-CH2-CH2), 1.85 (4 H, m, O-CH2-CH2), 2.88 (2 H, t, 3J = 7.4 Hz, SCH2),
4.08 (4 H, t, 3J = 6.5 Hz, OCH2), 4.29 (2 H, q, 3J = 7.1 Hz, O-CH2-CH3), 7.01 (2 H, d, 3J = 8.9, Ar-H),
7.21 (3 H, m, Ar-H), 7.40 (4 H, d, 3J = 8.7, Ar-H), 7.51 (1 H, t, 3J = 8.4, Ar-H), 8.17 (4 H, d, 3J = 8.8,
Ar-H), 8.30 (4 H, d, 3J = 8.7, Ar-H). 13C NMR: δC (CDCl3; 75 MHz): 14.1, 22.7, 26.0, 27.0, 29.1, 29.3,
29.35, 29.4, 29.55, 29.6, 29.65, 29.8, 30.9, 31.9, 34.0, 63.3, 65.1, 68.4, 68.3, 114.4, 115.8, 119.3, 120.9,
122.1, 126.6, 129.9, 131.8, 132.4, 151.4, 155.5, 163.8, 164.1, 164.3, 171.2. m/z (MALDI) 1025.26
[M+Li]+, C59H70LiO11S2 requires 1025.45.
1.4 Bent-core decorated gold nanoparticles Au1 and Au2
A fresh prepared solution of bent core thiol (BC10 or BC15), 1-hexanethiol and HAuCl4 [ratio (mmol)
= 1/1/1] in anhydrous THF was stirred for 10 minutes at room temperature under an atmosphere of dry
nitrogen gas. Thereafter, a fresh prepared solution of NaBH4 in deionized water [10 equivalents
(mmol)] was added at once. The initially bright yellow solution bubbled vigorously and turned quickly
to black with a precipitate forming. This mixture was then stirred for additional three hours at room
temperature, and hereafter the solvent was removed under reduced pressure. The gold nanoparticles
were then rigorously washed with ethyl acetate, acetonitrile, again ethyl acetate followed by diethyl
ether. Centrifugation and decantation followed by trying under mild vacuum yielded Au nanoparticles
1
with a 1:1 ratio of the two thiols coating the nanoparticle as judged by H NMR. Powder XRD
measurements confirmed the size measured from TEM (HR-TEM) images.
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2. POM images of selected bent-core derivatives
2.1. BC3 (unknown mesophase M2 on cooling below SmCPA phase)
SmCPA
M2
M2
SmCPA
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2.2 BC9 (texture of crystalline modification at 80 °C on cooling)
2.3 BC14 (texture of crystalline modification at 74 °C on cooling)
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1
3. H NMR spectra of Au1 (individual 1H NMR spectra and determination of thiol ratio)
Au1
Au2
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Supplementary material (ESI) for Journal of Materials Chemistry
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4. UV-vis spectra of Au1 and Au2
Au1 (SPRMax = 529 nm)
Au2 (SPRMax = 533 nm)
3
2.5
2
1.5
1.25
1
1.5
1
0.75
0.5
0.5
0
0.25
0
350 400 450 500 550 600 650 700 750 800
350 400 450 500 550 600 650 700 750 800
wavelength / nm
wavelength / nm
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5. DSC traces of BC9 and BC14
BC9
BC14
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6. DSC traces of Au1/BC1 and Au1/BC8 composites
a)
f)
g)
b)
h)
c)
d)
e)
i)
j)
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DSC traces acquired on the first round of heating and cooling at a rate of 10 °C/min of a) pure BC1,
and BC1 doped with b) 2.5 wt% Au1, c) 5 wt% Au1, d) 10 wt% Au1, and e) 15 wt% Au1, as well f)
pure BC8, and BC8 doped with g) 2.5 wt% Au1, h) 5 wt% Au1, i) 10 wt% Au1, and j) 15 wt% Au1.
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7. POM images of BC1 doped with 5wt% Au1 at VPP = 200V (crossed polarizers; different sign
of the applied electric field – snapshots during ac cycling)
(a)
```
(b)
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