Synthesis and characterization of novel jacketed polymers and investigation of their self assembly and application 3

3.1 Introduction Side chain LC polymers SCLCP with mesogenic groups laterally attached to the polymer backbone represent an interesting series of polymers.. In all cases, there are flexi

Chapter 3 Synthesis and characterization of novel terphenyl-

jacketed liquid crystalline polymers

3.1 Introduction

Side chain LC polymers (SCLCP) with mesogenic groups laterally attached to the polymer backbone represent an interesting series of polymers Compared with the conventional SCLCPs, polymer architectures with laterally attached groups give rise to the nematic phase 1 Wessflog et al reported the synthesis of lateral SCLCP in 1984 2, followed by many reports from functional poly(siloxanes), poly(acrylate), poly(norbornenes) derivatives 3-7 In all cases, there are flexible spacers incorporated with the mesogenic units on the polymer backbone Pugh et al.1,7-11 demonstrated that smectic layering could be induced in the SCLCPs with laterally attached mesogenic units The liquid crystalline polynorbornenes with 2, 5-bis[(4’-n-alkoxybenzoyl)oxy]benzyl mesogens can be forced into a smectic mesophase by terminating the alkoxy groups with fluorocarbon segments Due to the sharp immiscibility between the aliphatic polymer backbone and the n-perfluoroalkane, a layer type organization is formed from the micro-separation of the two components The immiscibility of n-alkanes and perfluoroalkanes is proportional to their lengths The polynorbornenes require at least eight carbon units in the terminated chains to organize into smectic layers Microseparation of the two components in these molecules is weak at the minimum lengths required for smectic layers7, 11 Lecommandoux et al.4-5 reported the synthesis of poly(siloxane) derivatives based on phenyl benzoate core terminated with alkyl chains They demonstrated that the polymer backbone could be segregated between the layers and also present at the middle part of the mesogenic layer, resulting to a smectic C mesophase

In 1987, Zhou et al.12-17 proposed a new side chain liquid crystalline polymers, in which mesogenic units are attached laterally to the backbone with very short spacers and

showed properties similar to that of the semi-rigid main chain liquid crystal polymers The lack of flexible spacers in the polymer lattice increased the range of observed mesophases 16-17 Percec et al.19-21 reported the synthesis of monodendron jacketed side chain liquid crystal polymers At low degree of polymerization (DP), the conical monodendrons assemble to produce a spherical polymer with a random-coil conformation for the polymer backbone With the increase of DPs, the monodendritic units are organized into cylindrical structures with extended polymer backbone The polymers self organize into hexagonal columnar (Φh) and cubic (Cub) lattice of the thermotropic mesophase

The strategy for making rigid polymers by incorporating many side groups on a flexible polymer backbone is interesting, owing to the interplay of strong steric interaction among the side groups and polymer backbone Such polymers show properties of semi-rigid main chain liquid crystal polymers with the rigidity can be adopted through tailoring the side-chains The organization of the rigid side group also allows to synthesize polymer with very narrow molecular weight distribution This new approach of synthesis of mesogenic polymer offers a rational design for the organized supramolecular materials 4,

22-23

Here, we report the synthesis of a series of polymers with laterally attached mesogenic units based on terphenyl groups with alkyl chains at the terminal position The terphenyl aromatic rigid core was used as mesogenic units to incorporate van der Waals interaction and shape effects of substituents on the polymer backbone At the same time polymers in which the mesogenic units are connected laterally to the polymer backbone without spacer or with very short spacer is expected to induce mesophase properties

3.2 Experimental section

3.2.1 Materials and reagents

All reagents and solvents were obtained from commercial sources and used without

further purification unless mentioned otherwise Tetrahydrofuran (THF) was distilled from metal sodium and benzophenone under N2 atmosphere N,N-dimethylformamide (DMF) was dried with 4 Å molecular sieves (Aldrich) Flash column chromatography was performed using silica gel (60-mesh, Aldrich) Dibenzoyl peroxide (BPO) was

recrystallized from chloroform-methanol solution as glistening crystals

3.2.2 Instrumentation

Fourier transform Infrared (IR) spectra were obtained using a Perkin-Elmer 1616

FT-IR spectrophotometer as KBr mulls 1 H NMR, 13 C NMR spectra were recorded on a Bruker ACF 300 MHz spectrometer MS spectra were obtained using a Finnigan TSQ

7000 spectrometer with ESI or EI ionization capabilities Thermogravimetric analyses (TGA) and differential scanning calorimetry (DSC) were conducted using a TA-SDT2960 and a TA-DSC 2920 at a heating rate of 10 °C min-1 under N2 environment Gel permeation chromatographic (GPC) analyses were done with a Waters 2696 separation module equipped with a Water 410 differential refractometer HPLC system and Waters Styragel HR 4E columns using THF as eluent and polystyrene as standard The XRD patterns were recorded on a powder diffractometer with a graphite monochromator using 1.54 Å Cu Kα wavelength at room temperature (scanning rate: 0.05 o/s; scan range 1.5-30o) A Zeiss Axiolab polarized optical microscope equipped with a Linkam LTS 350 hot stage was used to observe anisotropic textures

3.2.3 Synthesis

Poly (4, 5’, trimethoxy [1, 1’, 4’, 1”] terphenyl-2’-yl acrylate) (P1-C1), poly(4, dibutoxy-5’-methoxy [1, 1’, 4’, 1”] terphenyl-2’-yl acrylate) (P1-C4), poly(4, 4”- didecyloxy-5’-methoxy [1, 1’, 4’, 1”] terphenyl-2’-yl acrylate) (P1-C10), poly(1, 3-bis(4, 5’, 4”-trimethoxy[1, 1’, 4’,1”]terphenyl-2’-yloxy)-2-propyl acrylate) (P2-C1), poly(1, 3- bis(4, 4”-dibutoxy-5’-methoxy [1, 1’, 4’, 1”] terphenyl-2’-yloxy)-2-propyl acrylate) (P2- C4), and poly(1, 3-bis(4, 4”-didecyloxy-5’-methoxy [1, 1’, 4’,1”] terphenyl-2’-yloxy)-2- propyl acrylate) (P2-C10) were synthesized using the following route shown in Scheme 3.1

4”-OBn Br Br OCH3Br

Br

Br OH

OH

Br

Br OBn

OH

Br

Br OBn

6-C2 6-C10

8-C4 8-C10

P1-C1 P1-C4 P1-C10

R1=CH3

R1=C4H9

R1=C10H21

7-C4 7-C10

9-C4 9-C10

10-C4 10-C10

4-Methoxyphenyl boronic acid (5-C1)

In a 500 ml RB flask with a magnetic stirring bar was placed 9.35 g (50 mmol) of 4-C1

and 150 ml dry THF The solution was cooled to -78 °C and a 1.6 M solution of butyl lithium in hexanes (93 ml, 0.15 mol) was added slowly under nitrogen atmosphere The solution was warmed to RT and cooled to -78 °C, followed by the dropwise addition of triisopropyl borate (46 ml, 0.2 mol) during a period of 2 h After complete addition, the mixture was warmed to RT, stirred overnight, and mixed with 2 L of deionized water The organic phase was collected, dried with MgSO4, filtered, and concentrated under reduced pressure The light yellow solid was recrystallized from acetone Yield: 5.2 g (68.4 %) 1H NMR (300 MHz, DMSO-d6, δ ppm) 7.84 (s, B-OH, 2 H), 7.74-6.87 (m, ArH, 4 H), 3.75 (s, Ar-O-CH3, 3 H) 13C NMR (75.4 MHz, DMSO-d6, δ ppm) 160.8, 135.7, 112.8,108.3 (ArC), 54.7 (O-CH3) MS (ESI): m/z: 152, 134 Mp: 196 °C

4-Butoxyphenyl boronic acid (5-C4)

Compound 5-C4 was synthesized according to the procedure described for 5-C1 Yield:

10.3 g (44.2 %) 1H NMR (300 MHz, DMSO-d6, δ ppm) 7.80 (s, B-OH, 2 H), 7.73-6.85, (m, ArH, 4 H), 3.97 (t, J = 6.3Hz, Ar-O-CH2-, 2 H), 1.67 (p, J = 8.4Hz, R(O)-CH2-, 2 H), 1.42 (p, J = 8.1 Hz, -CH2-, 2 H), 0.92 (t, J = 7.2 Hz, 3 H) 13C NMR (75.4 MHz, DMSO-

d6, δ ppm) 160.3 136.8, 115.6, 113.5 (ArC), 66.7 (O-CH2-), 30.6, 18.6 (-CH2-), 13.6

(-CH3) MS (ESI): m/z: 194.0, 166.1 Mp: 167.5 °C

4-Decyloxyphenyl boronic acid (5-C10)

Compound C10 was synthesized according to the procedure described for compound C1 14.1g (45 mmol) of 1-bromo-4-decyloxybenzene (4-C10), 85 ml (0.135 mol) of 1.6

5-M butyllithilium in hexane and 41.4 ml (0.18 mol) of triisopropylborate were used and

the targeted compound was obtained as light yellow powder Yield: 11.8 g (31.4%) 1H NMR (300 MHz, DMSO-d6, δ ppm) 7.70 (d, J = 8.1 Hz, ArH, 2H), 7.56 (s, B-OH, 2H), 6.78 (d, J = 8.2 Hz, ArH, 2H), 3.92 (t, J = 6.3Hz, Ar-O-CH2-, 2 H), 1.72 (p, J = 6.3Hz, R(O)-CH2-, 2H), 1.24 (b, -CH2-, 14H), 0.84 (t, J = 6.0 Hz, 3H) 13C NMR (75.4 MHz, DMSO-d6, δ ppm) 158.2, 132.2, 116.3, 112.5 (ArC), 68.2 (O-CH2-), 31.8, 29.5, 29.4, 29.3 29.1, 25.9, 22.6, 22.0 (-CH2-), 13.8 (-CH3) MS (ESI): m/z: 278.2, 223.2, 210.2 Mp: 82.5 °C

5’-Benzyloxy-4, 2’, 4”-trimethoxy [1, 1’, 4’, 1”] terphenyl (6-C1) 24

A 250 ml round-bottomed flask equipped with a condenser was charged with 4.0g (11 mmol) of 1-benzyloxy-2, 5-dibromo-4-methoxybenzene and 4.3 g (28 mmol) of 4-methoxyphenyl boronic acid, 60 ml toluene, 20 ml methanol and 60 ml 2M sodium carbonate solution The mixture was degassed thoroughly, before the catalyst of 0.5g tetrakis(triphenylphosphine) palladium (2 mol%) was added in dark under argon atmosphere The reaction mixture was degassed once more and heated to 100 °C for 48 h

in argon atmosphere, cooled to RT, and filtered The liquid layer was separated with a separation funnel, and the aqueous layer was extracted with toluene (100 ml × 2), toluene fractions were combined, washed with 3 × 100 ml water, dried over MgSO4 and filtered After the removal of solvent under reduced pressure, the crude product obtained was purified using column chromatography on silica gel with hexane and dichloromethane (4:1) mixture as eluant Yield: 4.1g (44.3%) 1H NMR (300 MHz, DMSO-d6, δ ppm) 7.60

- 6.97 (m, ArH, 15 H), 4.99 (s, Ar-CH2-, 2 H), 3.86 (s, Ar-O-CH3, 6 H), 3.80 (s,

Ar-O-CH3, 3 H) 13C NMR (75.4 MHz, DMSO-d6, δ ppm) 158.7, 130.5, 130.4, 129.5, 129.4, 128.3, 127.5, 127.1, 117.4, 114.5, 114.2, 113.5, 113.4, 112.4 (ArC), 71.8 (O-CH2-), 56.2,

55.2 (O-CH3), 30.8 (O-CH3) MS (EI): m/z: 426.2, 335.1, 304.2, 277.1, 189.1 Mp: 148

°C

5’-Benzyloxy-4, 4”-dibutoxy-2’-methoxy [1, 1’, 4’, 1”] terphenyl (6-C4)

The synthesis of compound 6-C4 was performed according to the procedure for compound 6-C1 From 6.4 g (17.2 mmol) of compound 3 and 10 g (51.6 mmol) of compound 5-C4, the desired product was obtained as a white powder Yield: 7.2 g (81.9

%) 1H NMR (300 MHz, CDCl3, δ ppm) 7.63 - 7.00 (m, ArH, 15 H), 5.02 (s, Ar-CH2-, 2 H), 4.05 (t, J = 3.3 Hz, Ar-O-CH2-, 4 H), 3.82 (s, Ar-O-CH3, 3 H), 1.84 (b, -CH2-, 4 H), 1.55 (b, -CH2-, 4 H), 1.06 (t, J = 2.8 Hz, -CH3, 6 H) 13C NMR (75.4 MHz, CDCl3, δ ppm) 158.3, 151.1, 149.68, 137.4, 130.6, 130.5, 129.6, 129.5, 129.4, 129.3, 128.3, 127.5, 127.1, 118.5, 117.4, 115.3, 115.1, 114.3, 114.0, 113.3, 113.0 (ArC), 71.8 (O-CH2-Ar), 67.6 (O-

CH2-), 56.8 (O-CH3), 31.8, 19.2 (-CH2-), 13.8 (-CH3) MS (EI): m/z: 510.2, 419.2, 363.2, 307.1, 292.1, 199 Mp: 103 °C

5’-Benzyloxy-4, 4”-didecyloxy-2’-methoxy [1, 1’, 4’, 1”] terphenyl (6-C10)

The synthesis of compound 6-C10 was performed according to the procedure for compound 6-C1 From 4.1 g (11.0 mmol) of compound 3 and 9.2 g (33 mmol) of compound 5-C10 was obtained the desired product as a white powder Yield: 6.1 g (81.7

%) 1H NMR (300 MHz, CDCl3, δ ppm) 7.60-6.98 (m, ArH, 15 H), 5.00 (s, Ar-CH2-O, 2 H), 4.02 (t, J = 3.6 Hz, Ar-O-CH2-, 4 H), 3.80 (s, Ar-O-CH3, 3 H), 1.84 (p, J = 4.8, -CH2-, 4H), 1.34 (b, -CH2-, 28H), 0.92 (t, J = 6.0 Hz, -CH3, 6H) 13C NMR (75.4 MHz, CDCl3, δ ppm) 158.3, 151.1, 149.7, 137.4, 130.6, 130.5, 130.2, 129.4, 128.3, 127.5, 117.4, 115.1, 114.0, 112.9 (ArC), 71.8 (O-CH2-Ar), 67.9 (O-CH2-), 56.8 (O-CH3), 31.8, 29.5, 29.4,

29.3, 29.2, 26.0, 22.6, 19.2 (-CH2-), 13.8 (-CH3) MS (EI): m/z: 678.4, 588.4, 447.3, 308.1, 293.1, 247.0, 199 Mp: 77 °C

4, 5’, 4”-Trimethoxy [1, 1’, 4’, 1”] terphenyl-2’-ol (7-C1)

To a 100 ml round-bottom flask containing 10 % Pd/C (2.0 g) in 50 ml THF was added

compound 6-C1 (3.8 g, 8.9 mmol) The flask was purged with nitrogen, and a balloon

filled with H2 was fitted to the flask The nitrogen was briefly evacuated from the flask, and the H2 was charged above the solution The reaction mixture was stirred for 24 h at ambient temperature and then filtered The solid was washed with THF (3 × 25 ml), the organic phases were combined and the solvent was then removed under reduced pressure

to yield a white powder The resulting crude product was purified using column chromatography on silica gel with hexane and ethyl acetate (1:4) as the eluants Yield: 2.8 g (93.4 %) 1H NMR (300 MHz, CDCl3, δ ppm) 7.63 - 6.85 (m, ArH, 10 H), 4.93 (s, Ar-OH, 1 H), 3.88 (s, Ar-O-CH3, 6 H), 3.78 (s, Ar-O-CH3, 3 H) 13C NMR (75.4 MHz, CDCl3, δ ppm) 159.3, 158.7, 150.5, 146.4, 130.4, 130.2, 129.3, 126.6, 117.8, 114.6, 113.5, 112.5 (ArC), 56.3 (O-CH3), 54.3 (O-CH3) MS (EI): m/z: 336.1, 289.1, 261.0, 247.1, 213.1, 185.1 Mp: 161 °C

4, 4”-Dibutoxy-5’-methoxy [1, 1’, 4’, 1”] terphenyl-2’-ol (7-C4)

Compound C4 was synthesized according to the procedure described for compound C1 From 7.0 g (13.7 mmol) of 6-C4 was obtained the product as a white powder Yield:

7-5.4 g (93.6 %) 1H NMR (300 MHz, CDCl3, δ ppm) 7.52 - 6.94 (m, ArH, 10 H), 5.16 (s, Ar-OH, 1 H), 4.03 (t, J = 4.8 Hz, Ar-O-CH2-, 4 H), 3.74 (s, Ar-O-CH3, 3 H), 1.83 (b, -

CH2-, 4 H), 1.54 (b, -CH2-, 4 H), 1.02 (t, J = 6.3 Hz, -CH3, 6 H) 13C NMR (75.4 MHz, CDCl3, δ ppm) 158.8, 158.3, 150.5, 146.4, 130.4, 130.1, 129.0, 126.6, 117.4, 115.2,

113.6 (ArC), 67.8 (O-CH2-), 56.8 (O-CH3), 31.3, 19.2 (-CH2-), 13.8 (-CH3) MS (EI): m/z: 420.3, 364.3, 298.3, 242.2, 199.1, 186.2 Mp: 115 °C

4, 5’, 4”-Trimethoxy [1, 1’, 4’, 1”] terphenyl-2’-yl acrylate (8-C1)

Triethylamine (1.5 ml, 9 mmol) and compound 7-C1 (1.5 g, 4.46 mmol) were dissolved

in 30 ml dry THF placed in a 100 ml RB flask This solution was cooled to 0 °C, added a solution of acryloyl chloride (0.72 ml, 8.9 mmol) in 4 ml THF, warmed to room temperature and stirred for 4 h The mixture was then filtered and the volatile components were removed under reduced pressure The resulting crude product was dissolved in dichloromethane, washed with sodium bicarbonate solution, followed by water (3 × 50 ml) The organic layer was dried over anhydrous magnesium sulfate, filtered, and the excess solvent was removed under reduced pressure The crude product was further purified using flash column chromatography on silica gel column with hexane and ethyl acetate (1:1) as eluents to yield the monomer Yield: 1.4 g (80.4 %) 1H

NMR (300 MHz, CDCl3, δ ppm) 7.51 - 6.89 (m, ArH, 10 H), 6.90 (d, J = 14.0 Hz, C=CH,

1 H), 6.17 (q, J = 6.9 Hz, R=CH-, 1 H), 5.88 (d, J = 10.5 Hz, C=CH, 1 H), 3.78 (s,

Ar-O-CH3, 9H) 13CNMR (75.4 MHz, CDCl3, δ ppm) 165.2 (C=O), 158.7, 150.6, 149.3, 138.1, 137.8, 130.9, 130.7, 130.5, 130.4, 129.4, 129.3, 128.7, 128.2, 126.9, 125.8, 117.4, 117.1, 116.4, 116.1, 115.4, 115.0 (Ar-C, C=C), 57.2, 56.3 (O-CH3) MS (EI): m/z: 390.4, 279.2, 167.1, 149.1 Mp: 138 °C

4, 4”-Dibutoxy-5’-methoxy [1, 1’, 4’, 1”] terphenyl-2’-yl acrylate (8-C4)

Monomer 8-C4 was synthesized according to the procedure described for monomer 8-C1 From 1.85 g (4.4 mmol) of compound 7-C4, 0.90 ml (11 mmol) of acryloyl chloride, the

desired monomer was obtained Yield: 1.5 g (71.8 %) 1H NMR (300 MHz, CDCl3, δ ppm) 7.51-6.92 (m, ArH, 10H), 6.42 (d, J = 18.2 Hz, C=CH2, 1H), 6,17 (q, J =10.4 Hz, C=CH-, 1H), 5.88 (d, J = 11.7 Hz, C=CH2, 1H), 4.00 (t, J =3.9 Hz, O-CH2-, 4H), 3.82 (s, Ar-O-CH3, 3H), 1.79 (p, J = 6.9 Hz, R(O)-CH2-, 4H), 1.54 (p, J= 6.0 Hz, -CH2-, 4H), 0.99 (t, J= 7.5 Hz, -CH3, 6H) 13C NMR (75.4 MHz, CDCl3, δ ppm) 161.2 (C=O), 158.7, 158.2, 151.2, 150.4, 130.4, 129.7, 129.3, 128.9, 127.8, 118.0, 115.3, 114.3 (ArC), 69.6 (O-CH2-), 56.3 (O-CH3), 31.8, 29.5 (-CH2-), 13.4 (-CH3) MS (EI): m/z: 474.4, 420.3, 364.3, 307.2, 247.1, 199 Mp: 123 °C

4, 4”-Didecyloxy-5’-methoxy [1, 1’, 4’, 1”] terphenyl-2’-yl acrylate (8-C10)

Monomer C10 was synthesized according to the procedure described for monomer C1 From 1.4 g (2.4 mmol) of compound 7-C10, 0.58 ml (7 mmol) of acryloyl chloride

8-was obtained the desired monomer Yield: 0.9 g (58.9 %) 1H NMR (300 MHz, CDCl3, δ ppm) 7.52 - 6.96 (m, ArH, 10 H), 6.46 (d, J = 17.4 Hz, C=CH2, 1 H), 6,17 (q, J =10.4 Hz, C=CH-, 1 H), 5.89 (d, J = 11.4 Hz, C=CH2, 1 H), 4.02 (t, J = 3.9 Hz, Ar-O-CH2-, 4 H),

3.83 (s, Ar-O-CH3, 3 H), 1.82 (q, J = 6.6 Hz, -CH2-, 4H), 1.28 (b, -CH2-, 28 H), 0.91 (t, J

= 6.6 Hz, -CH3, 6 H) 13C NMR (75.4 MHz, CDCl3, δ ppm) 164.8 (C=O), 158.6, 158.4, 154.2, 140.9, 133.4, 132.1, 130.4, 129.9, 129.8, 129.6, 129.4, 127.7, 124.5, 115.3, 114.2, 114.0 (ArC), 68.0 (O-CH2-), 56.3 (O-CH3), 31.8, 29.5, 29.4, 29.3, 29.2, 26.0, 22.6, 18.6 (-CH2-), 13.9 (-CH3) MS (EI): m/z: 642.6, 588.6, 492.5, 438.5, 307.2, 298.2, 199.1 Mp:

45 °C

1, 3-Bis (4, 5’, 4”-trimethoxy [1, 1’, 4’, 1”] terphenyl-2’-yl)-propan-2-ol (9-C1)

To a 250 ml three neck RB flask fitted with a reflux condenser, addition funnel and a

nitrogen inlet, DMF (100 ml), compound 7-C1 (3.2 g, 9.5 mmol), potassium carbonate

(2.1 g, 15.2 mmol) and 0.05 g KI were added The mixture was purged with N2 for 30 min then stirred at 80 °C for 1 h under nitrogen atmosphere 1,3-dibromo-2-propanol (0.47 ml, 4.5 mmol) in 5 ml DMF was added dropwise using a dropping funnel The reaction mixture was stirred at 80 °C for 12 h and filtered The volatile components were removed under reduced pressure and excessive phenol was removed by washing with 2M sodium hydroxide and water (3 × 100 ml) The resulting crude product was purified using column chromatography on a silica gel column with a mixture of hexane and dichloromethane (2:3) as eluents Yield: 2.2 g (67.1 %) 1H NMR (300 MHz, CDCl3, δ ppm) 7.52 - 6.89 (m, ArH, 20H), 4.24 (q, J = 5.7 Hz, -CH(O)-, 1H), 3 (d, J = 5.2 Hz, O-

CH2-C, 4H), 3.86 (s, Ar-O-CH3, 3H), 3.78 (s, Ar-O-CH3, 3H), 3.77 (s, Ar-O-CH3, 3H), 2.20 (b, -C-OH, 1H) 13C NMR (75.4 MHz, CDCl3, δ ppm) 158.7, 151.2, 149.4, 131.4, 130.4, 129.7, 129.3, 114.6, 113.5, 112.5 (ArC), 70.5 (O-CH2-), 56.3, 55.2 (O-CH3), 36.8, (-CH-OH) MS (EI): m/z: 728.3, 670.2, 392.2, 336.1, 289.0, 213.0, 185.1 Mp: 178 °C

1, 3-Bis (4, 4”-dibutoxy-5’-methoxy [1, 1’, 4’, 1”] terphenyl-2’-yl) propan-2-ol (9-C4)

Compound C4 was synthesized according to the procedure described for compound C1 From 3.1 g (0.74 mmol) of compound 7-C4, 0.37 ml (3.6 mmol) of 1, 3-dibromo-

9-propan-2-ol was obtained the desired product Yield: 1.4 g (43.3 %) 1H NMR (300 MHz, CDCl3, δ ppm) 7.51 - 6.88 (m, ArH, 20 H), 4.22 (q, J = 4.7 Hz, -CH(O)-, 1 H), 4.04 (q, J

= 3.1 Hz, O-CH2-, 8 H), 3.95 (d, J = 4.2 Hz, O-CH2-C, 4 H), 3.78 (s, Ar-O-CH3, 6 H), 2.80 (d, -C-OH, 1 H) 13C NMR (75.4 MHz, CDCl3, δ ppm) 158.7, 158.2, 151.2, 150.4, 130.4, 128.9, 127.8, 118.0, 115.3, 114.3 (ArC), 70.5 (O-CH2-), 69.6 (O-CH2-C), 56.3 (O-

CH3), 36.8, (-CH-OH), 32.9, 19.2 (-CH2-), 13.8 (-CH3) MS (EI): m/z: 896.4, 838.5, 520.3, 476.3, 420.2, 364.2, 293.1, 199 Mp: 91 °C

1, 3-Bis (4, 4”-didecyloxy-5’-methoxy [1, 1’, 4’, 1”] terphenyl-2’-yl) propan-2-ol C10)

(Compound C10 was synthesized according to the procedure described for compound C1 From 3.07 g (5.2 mmol) of compound 7-C10, 0.27 ml (2.6 mmol) of 1,3-dibromide

9-propan-2-ol was obtained the desired product Yield: 1.5 g (46.8 %) 1H NMR (300 MHz, CDCl3, δ ppm) 7.51 - 6.84 (m, ArH, 20 H), 4.22 (q, J = 3.4 Hz, -CH(O)-, 1 H), 4.04-3.95 (m, O-CH2-, 12 H), 3.78 (s, Ar-O-CH3, 6 H), 2.28 (d, -C-OH, 1 H) 13CNMR (75.4 MHz, CDCl3, δ ppm) 158.7, 158.2, 151.2, 150.4, 130.4, 128.9, 127.8, 118.0, 115.3, 114.3 (ArC), 70.5 (O-CH2-), 69.6 (O-CH2-C), 56.3 (O-CH3), 36.8, (-CH-OH), 31.8, 29.5, 29.4, 29.3, 29.2, 26.0, 22.6, 18.8 (-CH2-), 13.4 (-CH3) MS (ESI): m/z: 1232.7, 644.5, 588.4, 448.2,

308 Mp: 78 °C

1, 3-Bis (4, 5’, 4”-trimethoxy [1, 1’, 4’, 1”] terphenyl-2’-yloxy)-2-propyl acrylate C1)

(10-Monomer 10-C1 was synthesized according to the procedure described for monomer C1 From 1.56 g (2.6 mmol) of compound 9-C1 and 0.63 ml (7.8 mmol) of acryloyl

8-chloride the desired monomer was obtained Yield: 1.1 g (5.4.0 %) 1H NMR (300 MHz, CDCl3, δ ppm) 7.52 - 6.82 (m, ArH, 20 H), 6.38 (d, J = 12.0, C=CH2, 1 H), 6.04 (q, J

=10.4, R=CH-, 1 H), 5.82 (d, J = 10.2, C=CH2, 1 H), 5.35 (t, J= 4.8 Hz, -CH(O)-, 1 H), 4.09 (d, J = 4.9, O-CH2-, 4 H), 3.78 (s, Ar-O-CH3, 18 H) 13C NMR (75.4 MHz, CDCl3, δ ppm) 165.2 (C=O), 158.7, 158.6, 151.2, 149.4, 131.4,130.4, 129.3, 128.9, 127.8, 118.0, 115.3, 112.3 (ArC), 70.7 (O-CH2-), 67.5 (O-CH2-C), 56.3 (O-CH3) MS (EI): m/z: 782.2, 724.4, 447.2, 375.2, 336.2, 213.1 Mp: 65 °C

1, 3-Bis (4, 4”-dibutoxy-5’-methoxy [1, 1’, 4’, 1”] terphenyl-2’-yloxy)-2-propyl acrylate (10-C4)

Monomer 10-C4 was synthesized according to the procedure described for monomer C1 From 1.1 g (1.2 mmol) of compound 9-C4, 0.3 ml (3.6 mmol) of acryloyl chloride

8-was obtained the desired monomer Yield: 0.85 g (74.4 %) 1H NMR (300 MHz, CDCl3,

δ ppm) 7.50 - 6.79 (m, ArH, 20 H), 6.35 (d, J = 15.9 Hz, C=CH2, 1 H), 6.07 (q, J =10.4

Hz, C=CH-, 1 H), 5.82 (d, J = 14.2 Hz, C=CH2, 1 H), 5.32 (t, J = 4.8 Hz, -CH(O)-, 1 H), 4.09 (b, J = 4.8 Hz, O-CH2-, 4 H), 4.05 (m, O-CH2-C, 8 H), 3.78 (s, Ar-O-CH3, 6 H), 1.81 (b, -CH2-, 8 H), 1.29 (b, -CH2-, 8 H), 0.87 (t, J = 6.0, -CH3, 12 H) 13C NMR (75.4 MHz, CDCl3, δ ppm) 165.1 (C=O), 158.7, 151.2, 150.4, 130.4, 130.1, 129.9, 129.5, 128.9, 127.8, 118.0, 115.3, 114.3 (ArC), 70.5 (O-CH2-), 69.6 (O-CH2-C), 56.3 (O-CH3), 32.9, 19.2 (-CH2-), 13.8 (-CH3) MS (EI): m/z: 951.2, 420.3, 307.2, 247.1, 199.1 Mp: 60 °C

1, 3-Bis (4, 4”-didecyloxy-5’-methoxy [1, 1’, 4’, 1”] terphenyl-2’-yloxy)-2-propyl acrylate (10-C10)