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Supplementary information

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Cyanobiphenyl-based liquid crystal dimers and the twist-bend nematic phase

Daniel A Paterson, Jordan P Abberley, William TA Harrison, John MD Storey, and Corrie T

Imrie*

Department of Chemistry, School of Natural and Computing Sciences, University of

Aberdeen, Meston Building, Aberdeen AB24 3UE, UK

*Author for correspondence; email [email protected]

mailto:[email protected]


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Section 1: Materials / General Methods/ Instrumentation S3

Section 2: Synthetic Procedures S5

Section 3: DSC Traces for CB5OCB S35

Section 4: References S36


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Section 1: Materials/ General methods/ Instrumentation

The synthesis of each group of dimers was prepared according to literature methods [1-7].

Only representative schemes are provided as the preparative methods were the same for all

homologues of the same series.

For reactions performed under anhydrous conditions all glassware was pre dried for at least

12 h in ovens set at 120 °C.

Materials

All reagents and solvents were available commercially and purchased from Sigma Aldrich, TCI

Chemicals or Alfa Aesar and were used as received unless otherwise stated. Anhydrous

solvents were purchased as anhydrous (over molecular sieves).

Solvents were evaporated at approximately 20 mm Hg using a water aspirator pump

connected to a Buchi rotary evaporator and trace solvents in a Thermo Scientific vacuum oven

at 1.0 mm Hg and 50 °C.

Column chromatography, was performing using silica gel grade 60A 40-63 micron, purchased

from Flurochem and a small neutral alumina plug was used at the base of the column to

remove ionic impurities where stated []. Reactions were monitored using Thin Layer

Chromatography (TLC) carried out on aluminium-backed plates with a coating of Merck

Kieselgel 60 F254 silica and an appropriate solvent system. Silica gel coated aluminium plates

were purchased from Merck KGaA. Spots were visualised using UV light (254 nm) or by

oxidation with either an aqueous permanganate dip or iodine.

General methods and instrumentation

Infrared spectra were recorded on a Thermo Scientific Nicolet IR100 FT-IR spectrometer with

an ATR diamond cell.

Mass spectra were recorded on a Waters QTOF Xevo G2 spectrometer.

Proton (1H) and carbon (13C) NMR spectra were recorded on a Varian Unity INOVA 400 MHz

NMR spectrometer with pulsed field gradients and waveform generator or a 300 MHz Bruker

Ultrashield NMR. The chemical shifts δ are quoted in parts per million (ppm) (SiMe4, d = 0),

using residual non-deuterated solvent signals as reference. Coupling constants (J values) are

quoted in Hertz (Hz) and are vicinal 3J, unless otherwise indicated. The splitting patterns are


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reported using the following abbreviations: b (broad), s (singlet), d (doublet), t (triplet), q

(quartet), quin (quintet), m (multiplet), and combinations thereof. 13C Spectra are proton

decoupled unless otherwise stated. Ar refers to an aromatic ring.

The purity of final products were verified using C,H,N microanalysis performed by the Micro

Analytical Laboratory in the School of Chemistry at the University of Manchester or the

Centre for Chemical Instrumental Analysis and Services at the University of Sheffield.


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Section 2: Synthetic procedures

2.1. Synthesis of 1-(4-cyanobiphenyl-4'-yloxy)-4-(4-cyanobiphenyl-4'-yl) butane,

CB4OCB

The synthetic route used to obtain 1-(4-cyanobiphenyl-4'-yloxy)-4-(4-cyanobiphenyl-4'-yl)

butane, CB4OCB, is shown in scheme 1;


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Scheme 1.

2.1.1. 4-Bromo-4'-(4-bromobutanoyl)biphenyl, 1

A solution of 4-bromobutyryl chloride (20.80 g, 0.11 mol) and 4-bromobiphenyl (26.13 g, 0.11

mol) in DCM (50 ml) was added dropwise to a stirred suspension of AlCl3 (14.68 g, 0.11 mol)

in DCM (50 ml) cooled to 0 °C in an ice bath. This mixture was warmed to room temperature

and stirred overnight. The reaction mixture was added to H2O (250 ml) and extracted using

DCM (2 x 80 ml). The organic fractions were combined and dried over anhydrous MgSO4

before the solvent was removed under vacuum. The crude product was purified using silica

gel chromatography with a petroleum ether (B.p. 40 – 60 °C) and DCM, 1:1 mixture as eluent,

R.f. 0.48. The crude product thus obtained was recrystallised from ethanol to give the title

compound as a white solid. Yield: 23.91 g, 57%. TCrI 109 °C. Infrared ν cm-1: 1675 (C=O), 1225,

1070, 811, 666, 529, 453. 1H NMR (400 MHz CDCl3)δ: 8.50 (2H, d, J 8.6 Hz, Ar), 7.65 (2H, d, J

8.6 Hz, Ar), 7.60 (2H, d, J 8.6 Hz, Ar), 7.49 (2H, d, J 8.6 Hz, Ar), 3.57 (2H, t, J 6.3 Hz, BrCH2CH2),

3.22 (2H, t, J 7.0 Hz, COCH2CH2), 2.34 (2H, quin, J 6.3 Hz, CH2CH2CH2). 13C NMR (100 MHz

CDCl3)δ: 198.29, 144.62, 138.72, 135.72, 132.12, 128.81, 128.73, 127.10, 122.70, 36.61, 33.61,

26.87.

2.1.2. 1-Bromo-4-(4'-bromobiphenyl-4-yl)butane, 2

Triethylsilane (22 ml, 0.14 mol) was added dropwise to a stirred solution of 1 (23.91 g, 0.063

mol) in TFA (33.5 ml, 0.44 mol) cooled in an ice bath, maintaining the temperature below 20

°C. The reaction mixture was stirred for 12 h at room temperature before being added to a

mixture of DCM (100 ml) and H2O (300 ml). The layers were separated and the aqueous layer

was washed with DCM (2 x 100 ml). The organic layers were combined and dried over

anhydrous MgSO4 before removing the solvent under vacuum. The crude product thus

obtained was recrystallised from EtOH to give the title compound as a white solid. Yield: 11.82

g, 51%. TCrI 102 °C. Infrared ν cm-1: 2922 (C-H), 1479, 1460, 1390, 1075, 1000, 805, 647, 640,

494, 485. 1H NMR (400 MHz CDCl3)δ: 7.55 (2H, d, J 8.5 Hz, Ar), 7.48 (2H, d, J 8.5 Hz, Ar), 7.43

(2H, d, J 8.5 Hz, Ar), 7.25 (2H, d, J 8.5 Hz, Ar), 3.44 (2H, t, J 6.2 Hz, BrCH2CH2), 2.69 (2H, t, J 7.4

Hz, ArCH2CH2), 1.93 (2H, quin, J 7.0 Hz, BrCH2CH2CH2CH2), 1.82 (2H, quin, J 7.1 Hz,

ArCH2CH2CH2CH2). 13C NMR (100 MHz CDCl3)δ: 141.39, 139.93, 137.65, 131.82, 128.94,

128.57, 126.92, 121.272, 34.59, 33.59, 32.22, 29.78.

2.1.3. 1-(4-Cyanobiphenyl-4’-yloxy)-4-(4-bromobiphenyl-4’-yl)butane, 3


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A mixture of 2 (6.28 g, 0.017 mol), 4-cyano-4'-hydroxybiphenyl (3.34 g, 0.017 mol), K2CO3

(4.66 g, 0.035 mol) and DMF (50 ml) was heated at reflux overnight. The reaction mixture was

cooled to room temperature, poured into H2O (150 ml), and the white precipitate was

collected by vacuum filtration. The crude product thus obtained was recrystallised from EtOAc

to give the title compound as a white solid. Yield: 4.40 g, 54%. TCrI 162 °C. Infrared ν cm-1: 2926

(C-H), 2225 (C≡N), 1600, 1492, 1482, 1471, 1291, 1248, 1176, 995, 828, 806, 797, 568, 536,

515. 1H NMR (400 MHz CDCl3)δ: 7.69 (2H, d, J 8.2 Hz, Ar), 7.62 (2H, d, J 8.2 Hz, Ar), 7.54 (2H,

d, J 8.2 Hz, Ar), 7.52 (2H, d, J 8.2 Hz, Ar), 7.48 (2H, d, J 8.2 Hz, Ar), 7.44 (2H, d, J 8.2 Hz, Ar),

7.28 (2H, d, J 8.2 Hz, Ar), 6.99 (2H, d, J 8.2 Hz, Ar), 4.04 (2H, t, J 6.3 Hz, OCH2CH2), 2.75 (2H, t,

J 7.8 Hz, ArCH2CH2), 1.88 (4H, m, OCH2CH2CH2). 13C NMR (100 MHz CDCl3)δ: 159.70, 145.23,

141.73, 139.95, 137.57, 132.57, 131.83, 131.35, 129.01, 128.55, 128.34, 127.06, 126.89,

121.26, 119.12, 115.08, 110.06, 67.88, 35.20, 28.82, 27.77.

2.1.4. 1-(4-Cyanobiphenyl-4'-yloxy)-4-(4-cyanobiphenyl-4'-yl)butane, 4

A mixture of 3 (3.93 g, 0.008 mol), CuCN (2.10 g, 0.022 mol) and dry NMP (50 ml) was heated

to 200 °C for 4 h under an argon atmosphere. The reaction mixture was cooled to 80 °C and

to this was added a solution of FeCl3 (7.03 g, 0.05 mol), H2O (15 ml) and 32 % HCl (6 ml) at 60

°C. This was allowed to cool slowly to room temperature and stirred overnight, then added to

a DCM (200 ml) and H2O (200 ml) mix. The aqueous layer was washed with DCM (100 ml). All

organic fractions were combined and washed with H2O (3 x 100 ml) before drying over

anhydrous MgSO4. Solvent was removed under vacuum to yield a brown liquid which was

added to H2O (200 ml). The brown precipitate was collected by vacuum filtration and washed

with H2O (400 ml). The crude product was purified by silica gel chromatography with a small

alumina plug and using DCM as eluent, R.f. 0.56. The crude product thus obtained was

recrystallised from EtOH to give the title compound as a fine white solid. Yield: 1.93 g, 56%.

TCrN 121 °C, TNTBN 103 °C, TNI 143 °C. Elemental analysis: Calculated for C30H24N2O: C, 84.08%,

H, 5.65%, N, 6.54%. Found: C, 83.68%, H, 5.65%, N, 6.61%. Infrared ν cm-1: 2923 (C-H), 2228

(C≡N), 1600, 1493, 1470, 1292, 1255, 1180, 1035, 995, 820, 547, 529. 1H NMR (400 MHz

CDCl3)δ: 7.71 (2H, d, J 8.2 Hz, Ar), 7.67 (2H, d, J 8.2 Hz, Ar), 7.64 (2H, d, J 8.2 Hz, Ar), 7.62 (2H,


6.98 (2H, d, J 8.2 Hz, Ar), 4.05 (2H, m, OCH2CH2), 2.78 (2H, m, ArCH2CH2), 1.88 (2H, m,

OCH2CH2CH2). 13C NMR (100 MHz CDCl3)δ: 159.67, 145.50, 145.20, 142.94, 136.75, 132.58,


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131.41, 129.21, 128.34, 127.49, 127.19, 127.07, 119.08, 119.00, 115.06, 110.63, 110.10,

67.84, 35.24, 28.82, 27.77. Overlapping peaks in the aromatic region of the 13C NMR mean

only 17 rather than 18 aromatic carbon peaks are observed. MS (ESI+, m/z): [M+Na]+

Calculated for C30H24N2ONa: 451.1786. Found: 451.1780.

2.2. Synthesis of 1-(4-cyanobiphenyl-4'-yloxy)-5-(4-cyanobiphenyl-4'yl)pentane,

CB5OCB

1-(4-cyanobiphenyl-4'yloxy)-5-(4-cyanobiphenyl-4'yl)pentane, CB5OCB, was synthesised in

the same manner as compound 4, the spectroscopic data for it and its intermediates are

provided.

2.2.1. 4-Bromo-4'-(5-bromopentanoyl)biphenyl, 5

This compound was synthesised according to the procedure described in 2.1.1. with a solution

of 5-bromovaleryl chloride (10.00 g, 0.054 mol) and 4-bromobiphenyl (12.58 g, 0.054 mol) in

DCM (50 ml) was added dropwise to a stirred suspension of AlCl3 (10.74 g, 0.081 mol) in DCM

(50 ml) cooled to 0 °C in an ice bath. This mixture was warmed to room temperature and

stirred overnight. The reaction mixture was added to H2O (250 ml) and extracted using DCM

(2 x 80 ml). The organic fractions were combined and dried over anhydrous MgSO4 before the

solvent was removed under vacuum. This product was purified by recrystallisation from EtOH

and obtained as a white solid. Yield: 15.28 g, 71%. TCrI 117 °C, TNI 62 °C. Infrared ν cm-1: 2925

(C-H), 1676 (C=O), 1604, 1275, 1186, 978, 812.1H NMR (300 MHz CDCl3)δ: 8.03 (2H, d, J 8.5

Hz, Ar), 7.65 (2H, d, J 8.5 Hz, Ar), 7.60 (2H, d, J 8.5 Hz, Ar), 7.49 (2H, d, J 8.5 Hz, Ar), 3.47 (2H,

t, J 6.3 Hz, BrCH2CH2), 3.04 (2H, t, J 6.8 Hz, COCH2CH2), 1.96 (4H, m, CH2CH2CH2CH2). 13C NMR

(75 MHz CDCl3)δ: 199.04, 144.47, 138.74, 135.82, 132.13, 128.82, 128.75, 127.09, 122.69,

37.51, 33.36, 32.21, 22.82.

2.2.2. 1-Bromo-5-(4'-bromobiphenyl-4-yl)pentane, 6

This compound was synthesised according to the procedure described in 2.1.2. with

triethylsilane (19.0 ml, 0.12 mol) was added dropwise to a stirred solution of 5 (15.28 g, 0.039






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anhydrous MgSO4 before removing the solvent under vacuum. This product was purified by

recrystallisation from EtOAc and obtained as a pink solid. Yield: 11.17 g, 75%. TCrI 79 °C.

Infrared ν cm-1: 2929 (C-H), 2854 (C-H), 1480, 1077, 999, 802, 558.1H NMR (300 MHz CDCl3)δ:

7.53 (2H, d, J 8.5 Hz, Ar), 7.46 (2H, d, J 8.5 Hz, Ar), 7.43 (2H, d, J 8.5 Hz, Ar), 7.23 (2H, d, J 8.5

Hz, Ar), 3.40 (2H, t, J 6.8 Hz, BrCH2CH2), 2.65 (2H, t, J 7.8 Hz, ArCH2CH2), 1.90 (2H, quin, J 7.4

Hz, BrCH2CH2CH2), 1.67 (2H, quin, J 7.8 Hz, ArCH2CH2CH2), 1.50 (2H, quin, J 8.0 Hz,

CH2CH2CH2CH2CH2). 13C NMR (75 MHz CDCl3)δ: 141.89, 139.97, 137.49, 131.79, 128.93,

128.54, 126.84, 121.22, 35.34, 33.74, 32.66, 30.55, 27.83.

2.2.3. 1-(4-Cyanobiphenyl-4’-yloxy)-5-(4-bromobiphenyl-4’-yl)pentane, 7

This compound was synthesised according to the procedure described in 2.1.3. with a mixture

of 6 (11.17 g, 0.029 mol), 4-cyano-4'-hydroxybiphenyl (5.70 g, 0.029 mol), K2CO3 (8.17 g, 0.059

mol) and DMF (30 ml) was heated at reflux overnight. The reaction mixture was cooled to

room temperature, poured into H2O (150 ml), and the white precipitate was collected by

vacuum filtration. This product was purified by recrystallisation initially from THF followed by

recrystallisation from EtOAc obtained as a white solid. Yield: 7.44 g, 52%. TCrN 203°C, TNI 224

°C. Infrared ν cm-1: 2925 (C-H), 2226 (C≡N), 1599, 1493, 1252, 1181, 999, 805, 531. 1H NMR

(300 MHz (2H, d, J 8.5 Hz, Ar), 7.48 (2H, d, J 8.5 Hz, Ar), 7.45 (2H, d, J 8.5 Hz, Ar), 7.27 (2H, d,

J 8.5 Hz, Ar), 6.99 (2H, d, J 8.5 Hz, Ar), 4.02 (2H, t, J 6.5 Hz, OCH2CH2), 2.70 (2H, t, J 7.6 Hz,

ArCH2CH2), 1.87 (2H, quin, J 7.4 Hz, OCH2CH2CH2), 1.75 (2H, quin, J 7.6 Hz, ArCH2CH2CH2), 1.59

(2H, m, CH2CH2CH2CH2CH2). 13C NMR (75 MHz CDCl3)δ: 159.71, 145.23, 142.05, 139.97,

137.45, 132.55, 131.80, 131.32, 128.95, 128.53, 128.32, 127.05, 126.81, 121.22, 119.10,

115.05, 110.05, 67.97, 35.46, 31.13, 29.09, 25.71.

2.2.4. 1-(4-Cyanobiphenyl-4'-yloxy)-5-(4-cyanobiphenyl-4'-yl)pentane, 8


of 7 (3.45 g, 0.0067 mol), CuCN (1.50 g, 0.017 mol) and dry NMP (50 ml) was heated to 200 °C

for 4 h under an argon atmosphere. The reaction mixture was cooled to 80 °C and to this was

added a solution of FeCl3 (7.03 g, 0.05 mol), H2O (15 ml) and 32 % HCl (6 ml) at 60 °C. This was

allowed to cool slowly to room temperature and stirred overnight, then added to a DCM (200

ml) and H2O (200 ml) mix. The aqueous layer was washed with DCM (100 ml). All organic

fractions were combined and washed with H2O (3 x 100 ml) before drying over anhydrous


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MgSO4. Solvent was removed under vacuum to yield a brown liquid which was added to H2O

(200 ml). The brown precipitate was collected by vacuum filtration and washed with H2O (400

ml). The crude product was purified by silica gel chromatography with a small alumina plug

and using DCM as eluent, R.f. 0.51. The crude product thus obtained was recrystallised from

EtOH to give the title compound as a white solid. Yield: 1.74 g, 57%. TCrN 182 °C, TNI 238 °C.

Elemental analysis: Calculated for C31H26N2O: C, 84.13%, H, 5.92%, N, 6.33%. Found: C,

84.07%, H, 6.04%, N, 6.24%. Infrared ν cm-1: 2925 (C-H), 2223 (C≡N), 1602, 1493, 1246, 1181,

995, 823, 806, 532. 1H NMR (300 MHz CDCl3)δ: 7.75 (8H, m, Ar), 7.59 (2H, d, J 7.6 Hz, Ar), 7.56

(2H, d, J 7.6 Hz, Ar), 7.35 (2H, d, J 7.6 Hz, Ar), 7.07 (2H, d, J 7.6 Hz, Ar), 4.14 (2H, t, J 6.2 Hz,

OCH2CH2), 2.76 (2H, t, J 7.5 Hz, ArCH2CH2), 1.92 (2H, quin, J 7.3 Hz, OCH2CH2CH2), 1.79 (2H,

quin, J 7.6 Hz, ArCH2CH2CH2), 1.59 (2H, quin, J 7.4 Hz, CH2CH2CH2CH2CH2). Relative insolubility

of the compound precluded the possibility of 13C NMR spectroscopy. MS (ESI+, m/z): [M+Na]+

Calculated for C31H26N2ONa: 465.1943. Found: 465.1939.

2.3. Synthesis of 1-(4-cyanobiphenyl-4'-yloxy)-6-(4-cyanobiphenyl-4'yl)hexane,

CB6OCB

1-(4-cyanobiphenyl-4'yloxy)-6-(4-cyanobiphenyl-4'yl)hexane, CB6OCB, was synthesised in the

same manner as compound 4, the spectroscopic data for it and its intermediates are provided.

2.3.1. 4-Bromo-4'-(6-bromohexanoyl)biphenyl, 9


of 6-bromohexanoyl chloride (24.18 g, 0.11 mol) and 4-bromobiphenyl (25.05 g, 0.11 mol) in





solvent was removed under vacuum. The crude product was purified using silica gel

chromatography with a petroleum ether (B.p. 40–60 °C) and DCM, 1:1 mixture as eluent, R.f.

0.45. The crude product thus obtained was recrystallised from EtOH to give the title

compound as a white solid. Yield: 22.70 g, 50%. TCrI 77 °C. Infrared ν cm-1: 2925 (C-H), 1679

(C=O), 1603, 1258, 1184, 971, 807, 665. 1H NMR (400 MHz CDCl3)δ: 7.96 (2H, d, J 8.7 Hz, Ar),

7.57 (2H, d, J 8.7 Hz, Ar), 7.52 (2H, d, J 8.7 Hz, Ar), 7.42 (2H, d, J 8.7 Hz, Ar), 3.37 (2H, t, J 6.7


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Hz, BrCH2CH2), 2.95 (2H, t, J 7.4 Hz, COCH2CH2), 1.87 (2H, quin, J 6.7 Hz, CH2CH2CH2CH2), 1.73

(2H, quin, J 7.4 Hz, CH2CH2CH2CH2), 1.49 (2H, m, CH2CH2CH2CH2CH2). 13C NMR (100 MHz

CDCl3)δ: 199.45, 144.39, 138.78, 135.94, 132.10, 128.81, 128.72, 127.06, 122.64, 38.35, 33.61,

32.62, 27.87, 23.35.

2.3.2. 1-Bromo-6-(4'-bromobiphenyl-4-yl)hexane, 10









g, 51%. TCrI 77 °C. Infrared ν cm-1: 2928 (C-H), 2854 (C-H), 1479, 1077, 1000, 804, 646, 503. 1H

NMR (400 MHz CDCl3)δ: 7.54 (2H, d, J 8.5 Hz, Ar), 7.47 (2H, d, J 8.5 Hz, Ar), 7.44 (2H, d, J 8.5

Hz, Ar), 7.25 (2H, d, J 8.5 Hz, Ar), 3.41 (2H, t, J 6.6 Hz, BrCH2CH2), 2.65 (2H, t, J 7.3 Hz,

ArCH2CH2), 1.87 (2H, quin, J 7.8 Hz, BrCH2CH2CH2), 1.67 (2H, quin, J 7.4 Hz, ArCH2CH2CH2), 1.48

(2H, m, CH2CH2CH2CH2), 1.39 (2H, m, CH2CH2CH2CH2). 13C NMR (100 MHz CDCl3)δ: 142.18,

140.02, 137.41, 131.79, 128.94, 128.55, 126.81, 121.20, 35.41, 33.93, 32.71, 31.18, 28.28,

28.01.

2.3.3. 1-(4-Cyanobiphenyl-4’-yloxy)-6-(4-bromobiphenyl-4’-yl)hexane, 11





vacuum filtration. The crude product thus obtained was recrystallised from EtOAc to give the

title compound as a white solid. Yield: 2.19 g, 33%. TCrI 142 °C, TNI 120 °C. Infrared ν cm-1: 2922

(C-H), 2222 (C≡N), 1602, 1493, 1481, 1249, 1001, 823, 805, 535, 506. 1H NMR (400 MHz




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6.97 (2H, d, J 8.5 Hz, Ar), 4.00 (2H, t, J 6.3 Hz, OCH2CH2), 2.67 (2H, t, J 7.8 Hz, ArCH2CH2), 1.82

(2H, quin, J 7.8 Hz, OCH2CH2CH2), 1.69 (2H, quin, J 7.5 Hz, ArCH2CH2CH2), 1.53 (2H, m,

CH2CH2CH2CH2), 1.45 (2H, m, CH2CH2CH2CH2). 13C NMR (100 MHz CDCl3)δ: 159.76, 145.24,

142.27, 140.00, 137.37, 132.57, 131.80, 131.28, 128.98, 128.53, 128.34, 127.06, 126.79,

121.20, 119.12, 115.08, 110.05, 68.04, 35.46, 31.29, 29.11, 28.92, 25.90.

2.3.4. 1-(4-Cyanobiphenyl-4'-yloxy)-6-(4-cyanobiphenyl-4'-yl)hexane, 12


of 11 (4.14g, 0.008 mol), CuCN (1.88 g, 0.021 mol) and dry NMP (70 ml) was heated to 200 °C







(200 ml). The brown precipitate was collected by vacuum filtration and washed with H2O (400

ml). The crude product was purified by silica gel chromatography with a small alumina plug

and using DCM as eluent, R.f. 0.54. The crude product thus obtained was recrystallised from

EtOH to give the title compound as a white solid. Yield: 1.98 g, 43%. TCrNTB 99 °C, TNTBN 109 °C,

TNI 155 °C. Elemental analysis: Calculated for C32H28N2O: C, 84.14%, H, 6.18%, N, 6.14%. Found:

C, 84.41%, H, 6.21%, N, 6.17%. Infrared ν cm-1: 2925 (C-H), 2219 (C≡N), 1601, 1493, 1471,

1250, 1174, 817, 807, 563, 525. 1H NMR (400 MHz CDCl3)δ: 7.70 (2H, d, J 8.3 Hz, Ar), 7.67 (2H,



Hz, OCH2CH2), 2.69 (2H, t, J 7.8 Hz, ArCH2CH2), 1.83 (2H, quin, J 7.8 Hz, OCH2CH2CH2), 1.70 (2H,

quin, J 7.4 Hz, ArCH2CH2CH2), 1.53 (2H, m, CH2CH2CH2CH2), 1.45 (2H, m, CH2CH2CH2CH2). 13C

NMR (100 MHz CDCl3)δ: 159.76, 145.89, 145.53, 143.38, 137.37, 133.27, 133.23, 131.81,

129.56, 128.67, 127.98, 127.77, 119.12, 119.09, 117.05, 110.44, 110.21, 68.05, 35.64, 31.27,

29.11, 28.99, 25.91. Overlapping peaks in the aromatic region of the 13C NMR mean only 17

rather than 18 aromatic carbon peaks are observed. MS (ESI+, m/z): [M+Na]+ Calculated for

C32H28N2ONa: 479.2099. Found: 479.2094. [2]


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2.4. Synthesis of 1-(4-cyanobiphenyl-4'-yloxy)-8-(4-cyanobiphenyl-4'yl)octane,

CB8OCB

1-(4-cyanobiphenyl-4'yloxy)-8-(4-cyanobiphenyl-4'yl)octane, CB8OCB, was synthesised in the

same manner as compound 4, with the exception that the acid chloride starting material had

to be synthesised from the required carboxylic acid. Synthetic details for this step are

reported. The spectroscopic data for CB8OCB and its intermediates are provided.

The synthetic route used to obtain 8-bromooctanoyl chloride, is shown in scheme 2;

Scheme 2.

2.4.1. 8-Bromooctanoyl chloride

A solution of 8-bromooctanoic acid (10.00 g, 0.045 mol), thionyl chloride (4 ml, 0.054 mol)

and chloroform (10 ml) was heated at 60 °C for 2 h. Chloroform and excess thionyl chloride

were then removed via vacuum distillation to yield a clear yellow liquid which was used

without further purification. Yield: 10.54 g, 97%.

2.4.2. 4-Bromo-4'-(8-bromooctanoyl)biphenyl, 13


of 8-bromohexanoyl chloride (4.23 g, 0.018 mol) and 4-bromobiphenyl (4.09 g, 0.018 mol) in






chromatography with a petroleum ether (B.p. 40–60 °C) and DCM, 1:1 mixture as eluent, R.f.

0.45. The crude product thus obtained was recrystallised from EtOH to give the title

compound as a white solid. Yield: 5.00 g, 65%. TCrI 56 °C, TNI 44 °C. Infrared ν cm-1: 2928 (C-H),

1675 (C≡N), 1603, 1480, 1238, 1077, 1001, 809, 782. 1H NMR (300 MHz CDCl3)δ: 8.04 (2H, d,

J 8.6 Hz, Ar), 7.65 (2H, d, J 8.6 Hz, Ar), 7.61 (2H, d, J 8.6 Hz, Ar), 7.50 (2H, d, J 8.6 Hz, Ar), 3.42


S14

(2H, t, J 6.8 Hz, BrCH2CH2), 3.00 (2H, t, J 7.4 Hz, COCH2CH2), 1.88 (2H, quin, J 7.4 Hz,

CH2CH2CH2CH2), 1.78 (2H, quin, J 7.3 Hz, CH2CH2CH2CH2), 1.42 (6H, m, CH2CH2CH2). 13C NMR

(75 MHz CDCl3)δ: 199.90, 144.33, 138.84, 136.05, 132.11, 128.82, 128.76, 127.05, 122.63,

38.58, 33.97, 32.74, 29.16, 28.63, 28.02, 24.24.

24.3. 1-Bromo-8-(4'-bromobiphenyl-4-yl)octane, 14









g, 66%. TCrI 65 °C. Infrared ν cm-1: 2926 (C-H), 2854 (C-H), 1480, 1389, 1076, 1000, 806, 494.

1H NMR (300 MHz CDCl3)δ: 7.57 (2H, d, J 8.3 Hz, Ar), 7.50 (2H, d, J 8.3 Hz, Ar), 7.47 (2H, d, J

8.3 Hz, Ar), 7.28 (2H, d, J 8.3 Hz, Ar), 3.43 (2H, t, J 6.8 Hz, BrCH2CH2), 2.66 (2H, t, J 7.7 Hz,


(2H, m, CH2CH2CH2CH2), 1.39 (6H, m, CH2CH2CH2). 13C NMR (75 MHz CDCl3)δ: 142.46, 140.07,

137.34, 131.81, 128.97, 128.57, 126.80, 121.18, 35.58, 34.06, 32.81, 31.41, 29.31, 29.20,

28.70, 28.16.

2.4.4. 1-(4-Cyanobiphenyl-4’-yloxy)-8-(4-bromobiphenyl-4’-yl)octane, 15





vacuum filtration. The crude product thus obtained was recrystallised from EtOAc to give the

title compound as a white solid. Yield: 1.61 g, 41%. TCrI 145 °C, TNTBN 100 °C TNI 132 °C. Infrared

ν cm-1: 2923 (C-H), 2852 (C-H), 2225 (C≡N), 1600, 1494, 1474, 1253, 1183, 824, 811, 530, 521.


8.8 Hz, Ar), 7.54 (2H, d, J 8.8 Hz, Ar), 7.50 (2H, d, J 8.8 Hz, Ar), 7.47 (2H, d, J 8.8 Hz, Ar), 7.28


S15

(2H, d, J 8.8 Hz, Ar), 7.01 (2H, d, J 8.8 Hz, Ar), 4.02 (2H, t, J 6.5 Hz, OCH2CH2), 2.67 (2H, t, J 7.7

Hz, ArCH2CH2), 1.84 (2H, quin, J 6.6 Hz, OCH2CH2CH2), 1.68 (2H, quin, J 6.5 Hz, ArCH2CH2CH2),

1.50 (2H, m, CH2CH2CH2CH2), 1.40 (6H, m, CH2CH2CH2). 13C NMR (75 MHz CDCl3)δ: 159.81,

145.28, 142.48, 140.06, 137.33, 132.57, 131.81, 131.29, 128.97, 128.55, 128.33, 127.07,

126.78, 121.20, 119.13, 115.10, 110.07, 68.16, 35.58, 31.40, 29.40, 29.27, 29.21, 26.02.

2.4.5. 1-(4-Cyanobiphenyl-4'-yloxy)-8-(4-cyanobiphenyl-4'-yl)octane, 16


of 15 (1.61 g, 0.003 mol), CuCN (0.65 g, 0.007 mol) and dry NMP (30 ml) was heated to 200 °C







(200 ml). The crude product was purified by silica gel chromatography with a small alumina

plug and using DCM as eluent, R.f. 0.39. The crude product thus obtained was recrystallised

from EtOH to give the title compound as a white solid. Yield: 0.41 g, 28%. TCrN 112 °C, TNTBN

108 °C, TNI 154 °C. Elemental analysis: Calculated for C34H32N2O: C, 84.26%, H, 6.66%, N, 5.78%.

Found: C, 84.42%, H, 6.66%, N, 5.77%. Infrared ν cm-1: 2924, 2852, 2222, 1600, 1493, 1251,

1177, 815, 563, 532. 1H NMR (300 MHz CDCl3)δ: 7.70 (8H, m, Ar), 7.55 (2H, d, J 8.6 Hz, Ar),


Hz, OCH2CH2), 2.69 (2H, t, J 7.7 Hz, ArCH2CH2), 1.83 (2H, quin, J 6.5 Hz, OCH2CH2CH2), 1.68 (2H,

quin, J 6.5 Hz, ArCH2CH2CH2), 1.50 (2H, quin, J 7.4 Hz CH2CH2CH2CH2), 1.40 (6H, m, CH2CH2CH2).

13C NMR (75 MHz CDCl3)δ: 159.80, 145.60, 145.26, 143.71, 136.50, 132.57, 131.31, 129.19,

128.33, 127.48, 127.10, 127.07, 119.11, 119.03, 115.09, 110.57, 110.09, 68.14, 35.62, 31.36,

29.41, 29.23, 29.30, 29.23, 29.22, 26.03. Overlapping peaks in the aromatic region of the 13C

NMR mean only 17 rather than 18 aromatic carbon peaks are observed. MS (ESI+, m/z):

[M+Na]+ Calculated for C34H32N2ONa: 507.2414. Found: 507.2406.


S16

2.5. Synthesis of 1-(4-cyanobiphenyl-4'-yloxy)-10-(4-cyanobiphenyl-4'yl)decane,

CB10OCB

1-(4-cyanobiphenyl-4'yloxy)-10-(4-cyanobiphenyl-4'yl)decane, CB10OCB, was synthesised in

the same manner as compound 4, with the exception that the acid chloride starting material

had to be synthesised from the required carboxylic acid. Synthetic details for this step are

reported in 2.3.6.1.. The spectroscopic data for CB10OCB and its intermediates are provided.

2.5.1. 10-Bromodacanoyl chloride


of 10-bromodecanoic acid (10.00 g, 0.04 mol), thionyl chloride (4 ml, 0.054 mol) and

chloroform (10 ml) was heated at 60 °C for 2 h. Chloroform and excess thionyl chloride were

then removed via vacuum distillation to yield a clear yellow liquid which was used without

further purification. Yield: 10.13 g, 94%.

2.5.2. 4-Bromo-4'-(10-bromodecanoyl)biphenyl, 17


of 10-bromodecanoyl chloride (10.13 g, 0.04 mol) and 4-bromobiphenyl (9.51 g, 0.04 mol) in






chromatography with a petroleum ether (B.p. 40–60 °C) and dichloromethane, 1:1 mixture as

eluent, R.f. 0.43. The crude product thus obtained was recrystallised from an EtOH and EtOAc

2:1 mix to give the title compound as a white solid. Yield: 14.87 g, 74%. TCrI 96 °C. Infrared ν

cm-1: 2929 (C-H), 2854 (C-H), 1675 (C=O), 1602, 1466, 1194, 1000, 973, 810, 728, 563. 1H NMR

(300 MHz CDCl3)δ: 8.05 (2H, d, J 8.7 Hz, Ar), 7.66 (2H, d, J 8.7 Hz, Ar), 7.62 (2H, d, J 8.7 Hz, Ar),

7.51 (2H, d, J 8.7 Hz, Ar), 3.43 (2H, t, J 6.9 Hz, BrCH2CH2), 3.01 (2H, t, J 7.4 Hz, COCH2CH2), 1.87

(2H, quin, J 7.1 Hz, CH2CH2CH2CH2), 1.78 (2H, quin, J 7.2 Hz, CH2CH2CH2CH2), 1.42 (10H, m,

CH2CH2CH2). 13C NMR (75 MHz CDCl3)δ: 200.03, 144.27, 138.83, 136.05, 132.11, 128.83,

128.78, 127.04, 122.64, 38.69, 34.05, 32.81, 29.38, 29.33, 29.30, 28.72, 28.15, 24.38.


S17

2.5.2. 1-Bromo-10-(4'-bromobiphenyl-4-yl)decane, 18


triethylsilane (5.8 ml, 0.035 mol) was added dropwise to a stirred solution of 17 (1.65 g,

0.0035 mol) in TFA (1.8 ml, 0.023 mol) cooled in an ice bath, maintaining the temperature

below 20 °C. The reaction mixture was stirred for 12 h at room temperature before being

added to a mixture of DCM (100 ml) and H2O (300 ml). The layers were separated and the

aqueous layer was washed with DCM (2 x 100 ml). The organic layers were combined and

dried over anhydrous MgSO4 before removing the solvent under vacuum. The crude product

thus obtained was recrystallised from EtOAc to give the title compound as a white solid. Yield:

1.00 g, 63%. TCrI 68 °C. Infrared ν cm-1: 2965 (C-H), 1584, 1472, 1387, 1079, 996, 807, 688,


d, J 8.5 Hz, Ar), 7.27 (2H, d, J 8.5 Hz, Ar), 3.43 (2H, t, J 6.9 Hz, BrCH2CH2), 2.66 (2H, t, J 7.7 Hz,


(2H, m, CH2CH2CH2CH2), 1.39 (10H, m, CH2CH2CH2).

2.5.4. 1-(4-Cyanobiphenyl-4’-yloxy)-10-(4-bromobiphenyl-4’-yl)decane, 19





vacuum filtration. The crude product thus obtained was recrystallised from an EtOH and

EtOAc 1:1 mix to give the title compound as a white solid. Yield: 0.82 g, 66%. TCrI 137 °C, TNTBN

101 °C TNI 134 °C. Infrared ν cm-1: 2920 (C-H), 2851 (C-H), 2222 (C≡N), 1603, 1493, 1473, 1244,

1177, 1001, 830, 809, 535. 1H NMR (300 MHz CDCl3)δ: 7.71 (2H, d, J 8.6 Hz, Ar), 7.66 (2H, d, J

8.6 Hz, Ar), 7.57 (2H, d, J 8.6 Hz, Ar), 7.55 (2H, d, J 8.6 Hz, Ar), 7.49 (2H, d, J 8.6 Hz, Ar), 7.47


OCH2CH2), 2.66 (2H, t, J 7.7 Hz, ArCH2CH2), 1.83 (2H, quin, J 6.6 Hz, OCH2CH2CH2), 1.66 (2H,

quin, J 7.2 Hz, ArCH2CH2CH2), 1.49 (2H, m, CH2CH2CH2CH2), 1.40 (10H, m, CH2CH2CH2). 13C NMR

(75 MHz CDCl3)δ: 159.80, 145.29, 142.57, 140.05, 137.30, 132.59, 132.12, 131.81, 131.26,

128.98, 128.57, 128.34, 127.09, 126.78, 121.18, 115.07, 110.03, 68.16, 35.62, 31.49, 31.48,

29.55, 29.49, 29.38, 29.33, 29.23, 26.04.


S18

2.5.4. 1-(4-Cyanobiphenyl-4'-yloxy)-10-(4-cyanobiphenyl-4'-yl)decane, 20


of 19 (0.82 g, 0.0015 mol), CuCN (0.35 g, 0.0036 mol) and dry NMP (50 ml) was heated to 200

°C for 4 h under an argon atmosphere. The reaction mixture was cooled to 80 °C and to this

was added a solution of FeCl3 (7.02 g, 0.05 mol), H2O (15 ml) and 32 % HCl (6 ml) at 60 °C. This

was allowed to cool slowly to room temperature and stirred overnight, then added to a DCM

(200 ml) and H2O (200 ml) mix. The aqueous layer was washed with DCM (100 ml). All organic



(200 ml). The crude product was purified by silica gel chromatography with a small alumina

plug and using DCM as eluent, R.f. 0.57. The crude product thus obtained was recrystallised

from EtOH to give the title compound as a white solid. Yield: 0.23 g, 30%. TCrN 116 °C, TNTBN

107 °C, TNI 148 °C. Elemental analysis: Calculated for C36H36N2O: C, 84.34%, H, 7.08%, N, 5.46%.

Found: C, 84.36%, H, 6.97%, N, 5.42%. Infrared ν cm-1: 2921 (C-H), 2852 (C-H), 2223 (C≡N),

1600, 1493, 1251, 1177, 816, 530, 522. 1H NMR (300 MHz CDCl3)δ: 7.69 (8H, m, Ar), 7.53 (2H,


4.01 (2H, t, J 6.6 Hz, OCH2CH2), 2.67 (2H, t, J 7.7 Hz, ArCH2CH2), 1.82 (2H, quin, J 7.0 Hz,

OCH2CH2CH2), 1.66 (2H, quin, J 7.2 Hz, ArCH2CH2CH2), 1.48 (2H, quin, J 7.4 Hz CH2CH2CH2CH2),

1.34 (10H, m, CH2CH2CH2). 13C NMR (75 MHz CDCl3)δ: 159.80, 145.61, 145.28, 143.78, 136.47,

132.58, 131.28, 129.20, 128.33, 127.48, 127.08, 119.13, 119.05, 115.09, 110.55, 110.07,

68.18, 35.65, 31.41, 29.55, 29.51, 29.49, 29.38, 29.31, 29.24, 26.05. Overlapping peaks in the

aromatic region of the 13C NMR mean only 16 rather than 18 aromatic carbon peaks are

observed. MS (ESI+, m/z): [M+Na]+ Calculated for C36H36N2ONa: 535.2725. Found: 535.2717.

2.6. Synthesis of 1,5-Bis(4'-cyanobiphenyl-4-yl)pentane, CB5CB

The synthetic route used to obtain 1,5-Bis(4'-cyanobiphenyl-4-yl)pentane, CB5CB, is shown

in scheme 3;


S19

Scheme 3.

2.6.1. 1,5-Bis(4'-bromobiphenyl-4-carbonyl)propane, 21

A solution of glutaryl chloride (8.45 g, 0.05 mol) and 4-bromobiphenyl (24.32 g, 0.10 mol) in



stirred overnight. The reaction mixture was added to H2O (250 ml) and the grey precipitate

collected by vacuum filtration. The crude product was used without further purification. Yield:

17.20 g, 31%. Infrared ν cm-1: 2923 (C-H), 1671 (C=O), 1602, 1346, 1250, 1000, 968, 808, 466.


S20

1H NMR (400 MHz DMSO-d6)δ: 8.06 (4H, d, J 8.8 Hz, Ar), 7.84 (4H, d, J 8.8 Hz, Ar), 7.71 (4H, d,

J 8.8 Hz, Ar), 7.69 (4H, d, J 8.8 Hz, Ar), 3.17 (4H, t, J 7.4 Hz, COCH2CH2), 2.01 (2H, quin,

CH2CH2CH2). Relative insolubility of the compound precluded the possibility of 13C NMR

spectroscopy.

2.6.2. 1,5-Bis(4'-bromobiphenyl-4-yl)pentane, 22

A mixture of KOH (3.09 g, 0.05 mol), ethylene diglycol (50 ml), hydrazine monohydrate (98%)

(2.30 g, 0.05mol) and 21 (7.02g, 0.012 mol) was heated at 140 °C for 5 h before being cooled

to room temperature and stirred overnight. Reaction mixture added to H2O (200 ml) and

extracted twice with DCM (2 X 100 ml), the organic layers were combined and further washed

with water (3 X 100 ml) before drying over anhydrous MgSO4. The solvent was removed via

rotary evaporation before product taken up in H2O and vacuum filtered to remove traces of

hydrazine and ethylene diglycol. The crude orange solid was used without further purification.

Yield: 3.41 g, 49%. Infrared ν cm-1: 2923 (C-H), 2854 (C-H), 1481, 1389, 1075, 998, 805, 489.

1H NMR (400 MHz DMSO-d6)δ: 8.01 (4H, d, J 8.7 Hz, Ar), 7.80 (4H, d, J 8.7 Hz, Ar), 7.72 (4H, d,

J 8.7 Hz, Ar), 7.69 (4H, d, J 8.7 Hz, Ar), 2.67 (4H, t, J 1.9 Hz, ArCH2CH2), 1.64 (4H, quin, J 7.7 Hz,

ArCH2CH2CH2CH2), 1.34 (2H, quin, J 5.2 Hz, CH2CH2CH2CH2CH2). Relative insolubility of the

compound precluded the possibility of 13C NMR spectroscopy.

2.6.3. 1,5-Bis(4'-cyanobiphenyl-4-yl)pentane, 23

A mixture of 22 (7.13 g, 0.013 mol), CuCN (3.49 g, 0.041 mol) and anhydrous NMP (60 ml)

was heated to 200 °C for 4 h under an argon atmosphere. The reaction mixture was cooled to

80 °C and to this a mixture of a solution of FeCl3 (7.63 g, 0.05 mol), H2O (15 ml) and 32% HCl

(6 ml) was added at 60 °C. This was allowed to cool to room temperature and stirred overnight

before adding to a H2O (250 ml) and DCM (250 ml) mix. The aqueous layer was washed with

DCM (100 ml), all organic layers were combined and washed with H2O (3 x 100 ml) before

drying over anhydrous MgSO4. The solvent was removed under vacuum to yield a brown liquid

which was added to H2O (200 ml). The brown precipitate was collected using vacuum filtration

and washed with copious amounts of H2O. The crude product was purified by silica gel column

chromatography using DCM as eluent, R.f. 0.52. The crude product thus obtained was

recrystallised from EtOH to give the title compound as a yellow solid. Yield: 0.31 g, 5%. TCrI

150 °C, TNTBN 92 °C, TNI 97 °C. Elemental analysis: Calculated for C31H26N2: C, 87.29%, H, 6.14%,

N, 6.57%. Found: C, 86.77%, H, 6.29%, N, 6.62%. Infrared ν cm-1: 2925 (C-H), 2852 (C-H), 2225


S21

(C≡N), 1602, 1491, 817, 554, 542. 1H NMR (400 MHz CDCl3)δ: 7.71 (4H, d, J 8.5 Hz, Ar), 7.67


ArCH2CH2), 1.71 (4H, quin, J 7.7 Hz, ArCH2CH2CH2CH2), 1.45 (2H, quin, J 7.7 Hz,


127.47, 127.13, 119.05, 110.56, 35.53, 31.29, 28.96. MS (ESI+, m/z): [M+Na]+ Calculated for

C31H26N2Na: 449.1994. Found: 449.1990.

2.7. 1,6-Bis(4'-cyanobiphenyl-4-yl)hexane, CB6CB

1,6-Bis(4'-cyanobiphenyl-4-yl)hexane was synthesised in the same manner as compound 23

with the exception of the reduction of the carbonyl, which was reduced using triethylsilane

and trifluoroacetic acid [1]. Spectroscopic data is given and agrees with previously reported

data [3].

2.7.1. 1,6-Bis(4'-bromobiphenyl-4-carbonyl)butane, 24


of adipoyl chloride (8.3 ml, 0.05 mol) and 4-bromobiphenyl (23.42 g, 0.10 mol) in DCM (50

ml) was added dropwise to a stirred suspension of AlCl3 (14.10 g, 0.10 mol) in DCM (50 ml)

cooled to 0 °C in an ice bath. This mixture was warmed to room temperature and stirred

overnight. The reaction mixture was added to H2O (250 ml) and the grey precipitate collected

by vacuum filtration. The crude product thus obtained was recrystallised from toluene to give

the title compound as a yellow crystals. Yield: 5.23 g, 68%. TCrI 245 °C, TNI 209 °C. Infrared ν

cm-1: 2926 (C-H), 1674 (C=O), 1603, 1387, 1261, 1190, 972, 809, 741. 1H NMR (400 MHz

DMSO-d6)δ: 8.03 (4H, d, J 8.6 Hz, Ar), 7.81 (4H, d, J 8.6 Hz, Ar), 7.69 (4H, d, J 8.6 Hz, Ar), 7.68

(4H, d, J 8.6 Hz, Ar), 3.04 (4H, t, J 6.6 Hz, COCH2CH2), 2.23 (4H, quin, J 7.0 Hz, CH2CH2CH2).

Relative insolubility of the compound precluded the possibility of 13C NMR spectroscopy.

The synthetic route used to obtain compound 25 is shown in scheme 4;


S22

Scheme 4.

2.7.2. 1,6-Bis(4'-bromobiphenyl-4-yl)hexane, 25

Triethylsilane (10.4 ml, 0.065 mol) was added dropwise to a stirred solution of 24 (5.23 g,

0.009 mol) in trifluoroacetic acid (15.6 ml, 0.20 mol) cooled in an ice bath, maintaining the

temperature below 20 °C. The reaction mixture was stirred for 48 h before being added to a




obtained was purified by recrystallization from EtOAc. Yield: 1.71 g, 35%. TCrI 220 °C. Infrared

ν cm-1: 2923 (C-H), 2853 (C-H), 1479, 1076, 1000, 807, 481. 1H NMR (400 MHz DMSO-d6)δ:

7.54 (4H, d, J 8.6 Hz, Ar), 7.47 (4H, d, J 8.6 Hz, Ar), 7.44 (4H, d, J 8.6 Hz, Ar), 7.24 (4H, d, J 8.6

Hz, Ar), 2.64 (4H, t, J 7.5 Hz, ArCH2CH2), 1.65 (4H, quin, J 5.5 Hz, ArCH2CH2CH2CH2), 1.41 (4H,

quin, J 3.5 Hz, CH2CH2CH2CH2CH2). 13C NMR (100 MHz CDCl3)δ: 142.42, 140.04, 131.79, 128.94,

128.54, 127.06, 126.76, 121.16, 35.54, 31.33, 29.13.

2.7.3. 1,6-Bis(4'-cyanobiphenyl-4-yl)hexane, 26


of 25 (1.93 g, 0.004 mol), CuCN (0.98 g, 0.011 mol) and anhydrous NMP (60 ml) was heated


to this a mixture of a solution of FeCl3 (6.97 g, 0.05 mol), H2O (15 ml) and 32% HCl (6 ml) was

added at 60 °C. This was allowed to cool to room temperature and stirred overnight before

adding to a H2O (250 ml) and DCM (250 ml) mix. The aqueous layer was washed with DCM

(100 ml), all organic layers were combined and washed with H2O (3 x 100 ml) before drying

over anhydrous MgSO4. The solvent was removed under vacuum to yield a brown liquid which

was added to H2O (200 ml). The brown precipitate was collected using vacuum filtration and

washed with copious amounts of H2O. The crude product was purified by silica gel column

chromatography using DCM as eluent, R.f. 0.54. The product was further purified by

recrystallisation from EtOH to yield a white solid. TCrN 132 °C, TNI 231 °C. Elemental analysis:

Calculated for C32H28N2: C, 87.24%, H, 6.41%, N, 6.36%. Found: C, 86.60%, H, 6.61%, N, 6.41%.

Infrared ν cm-1: 2926 (C-H), 2853 (C-H), 2230 (C≡N), 1604, 1493, 1181, 814, 771, 539, 515. 1H



S23

Hz, Ar), 7.27 (4H, d, J 8.4 Hz, Ar), 2.67 (4H, t, J 7.4 Hz, ArCH2CH2), 1.56 (4H, m,

ArCH2CH2CH2CH2), 1.45 (4H, m, CH2CH2CH2CH2CH2CH2). 13C NMR (100 MHz CDCl3)δ: 145.56,

143.61, 136.51, 132.56, 129.17, 127.47, 127.09, 119.02, 110.57, 35.59, 31.27, 29.13. MS (ESI+,

m/z): [M+Na]+ Calculated for C32H28N2Na: 463.2150. Found: 463.2148.

2.8. 1,7-Bis(4'-cyanobiphenyl-4-yl)heptane, CB7CB

1,7-Bis(4'-cyanobiphenyl-4-yl)heptane was synthesised in the same manner as compound 23

with the exception of the reduction of the carbonyl, the method for which is described in

2.7.2.. The synthetic details and spectroscopic data for CB7CB and its intermediates are

provided and agree with previously reported data [3,4].

2.8.1. 1,7-Bis(4'-bromobiphenyl-4-carbonyl)pentane, 27


of pimeloyl chloride (5.66 ml, 0.034 mol) and 4-bromobiphenyl (16.71 g, 0.072 mol) in DCM

(50 ml) was added dropwise to a stirred suspension of AlCl3 (9.07 g, 0.068 mol) in DCM (50

ml) cooled to 0 °C in an ice bath. This mixture was warmed to room temperature and stirred

overnight. The reaction mixture was added to H2O (250 ml) and the grey precipitate collected

by vacuum filtration. The crude product thus obtained was recrystallised from chloroform to

give the title compound as a white solid. Yield: 16.54 g, 77%. TCrI 217 °C. Infrared ν cm-1: 2922

(C-H), 1673 (C=O), 1603, 1346, 1251, 1189, 1002, 968, 805, 666, 456. 1H NMR (400 MHz

DMSO-d6)δ: 8.03 (4H, d, J 8.6 Hz, Ar), 7.81 (4H, d, J 8.6 Hz, Ar), 7.69 (4H, d, J 8.6 Hz, Ar), 7.68

(4H, d, J 8.6 Hz, Ar), 3.04 (4H, t, J 6.6 Hz, COCH2CH2), 1.75 (4H, m, COCH2CH2CH2), 1.42 (2H, m,

CH2CH2CH2). Relative insolubility of the compound precluded the possibility of 13C NMR

spectroscopy.

2.8.2. 1,7-Bis(4'-bromobiphenyl-4-yl)heptane, 28


triethylsilane (26.9 ml, 0.17 mol) added dropwise to a stirred solution of 27 (16.54 g, 0.026

mol) in trifluoroacetic acid (39.5 ml, 0.52 mol) cooled in an ice bath, maintaining the

temperature below 20 °C. The reaction mixture was stirred for 48 h before adding to a 100 ml

DCM and H2O (300 ml). The layers were separated and the aqueous layer was washed with

DCM (2 x 100 ml). The organic layers were combined and dried over anhydrous MgSO4 before

removing the solvent under vacuum. The crude product thus obtained was recrystallised from


S24

a 1:1.5 EtOH/EtOAc mixture to give the title compound as a white solid. Yield: 10.31 g, 66%.

TCrI 146 °C. Infrared ν cm-1: 2923 (C-H), 2853 (C-H), 1480, 1077, 1001, 805, 487. 1H NMR (400

MHz DMSO-d6)δ: 7.63 (4H, d, J 8.3 Hz, Ar), 7.60 (4H, d, J 8.3 Hz, Ar), 7.55 (4H, d, J 8.3 Hz, Ar),

7.26 (4H, d, J 8.3 Hz, Ar), 2.60 (4H, t, J 7.4 Hz, ArCH2CH2), 1.58 (4H, m, ArCH2CH2CH2CH2), 1.31

(6H, m, CH2CH2CH2CH2CH2). 13C NMR (100 MHz CDCl3)δ: 142.49, 140.06, 137.32, 131.81,

128.97, 128.55, 126.78, 121.18, 35.56, 31.37, 29.30, 29.17.

2.8.3. 1,7-Bis(4'-cyanobiphenyl-4-yl)heptane, 29




to this a mixture of a solution of FeCl3 (13.98 g, 0.10 mol), H2O (30 ml) and 32% HCl (12 ml)

was added at 60 °C. This was allowed to cool to room temperature and stirred overnight






chromatography using DCM as eluent, R.f. 0.56. The product was further purified by

recrystallisation from EtOH to yield a white solid. This product was purified by flash

chromatography using DCM as eluent, before recrystallisation from EtOH to yield off white

crystals. Yield: 3.70 g, 44%. TCrNTB 102 °C, TNTBN 103 °C, TNI 114 °C. Elemental analysis:


Infrared ν cm-1: 2922 (C-H), 2852 (C-H), 2230 (C≡N), 1604, 1494, 1467, 1186, 819, 801, 553,


d, J 8.5, Ar), 7.28 (4H, d, J 8.5 Hz, Ar), 2.66 (4H, t, J 7.4 Hz, ArCH2CH2), 1.65 (4H, m,

ArCH2CH2CH2CH2), 1.45 (6H, m, CH2CH2CH2CH2CH2). 13C NMR (100 MHz CDCl3)δ: 145.57,

143.67, 136.49, 132.56, 129.16, 127.46, 127.07, 119.01, 110.57, 35.59, 31.34, 29.33, 29.20.

MS (ESI+, m/z): [M+Na]+ Calculated for C33H30N2Na: 477.2307. Found: 477.2302.


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2.9. 1,9-Bis(4'-cyanobiphenyl-4-yl)nonane, CB9CB

1,9-Bis(4'-cyanobiphenyl-4-yl)nonane was synthesised in the same manner as compound 23

with the exception of the reduction of the carbonyl, the method for which is described in

2.7.2.. The synthetic details and spectroscopic data for CB9CB and its intermediates are

provided and agree with previously reported data [5].

2.9.1. 1,9-Bis(4'-bromobiphenyl-4-carbonyl)heptane, 30


of azelaoyl chloride (5.00 ml, 0.026 mol) and 4-bromobiphenyl (12.56 g, 0.054 mol) in DCM

(40 ml) was added dropwise to a stirred suspension of AlCl3 (7.14 g, 0.054 mol) in DCM (40

ml) cooled to 0 °C in an ice bath. This mixture was warmed to room temperature and stirred

overnight. The reaction mixture was added to H2O (250 ml) and the white precipitate

collected by vacuum filtration. The crude product thus obtained was a white solid used

without purification as nmr showed a pure enough to take forward. Yield: 13.84 g, 86%. TCrI

205 °C. Infrared ν cm-1: 2934 (C-H), 2921 (C-H), 1674 (C=O), 1603, 1480, 1237, 1085, 983,

816, 766, 454. 1H NMR (300 MHz CDCl3)δ: 8.05 (4H, d, J 8.4 Hz, Ar), 7.66 (4H, d, J 8.4 Hz, Ar),

7.62 (4H, d, J 8.4 Hz, Ar), 7.51 (4H, d, J 8.4 Hz, Ar), 3.02 (4H, t, J 7.0 Hz, COCH2CH2), 1.79 (4H,

m, COCH2CH2CH2), 1.45 (6H, m, CH2CH2CH2). Relative insolubility of the compound precluded

the possibility of 13C NMR spectroscopy.

2.9.2. 1,9-Bis(4'-bromobiphenyl-4-yl)nonane, 31








EtOAc to give the title compound as a white solid. Yield: 9.65 g, 74%. TCrI 117 °C. Infrared ν

cm-1: 2923 (C-H), 2850 (C-H), 1480, 1389, 1075, 1000, 811, 795, 502. 1H NMR (300 MHz


d, J 8.0 Hz, Ar), 2.67 (4H, t, J 7.7 Hz, ArCH2CH2), 1.67 (4H, quin, J 7.0 Hz, ArCH2CH2CH2CH2),


S26

1.35 (10H, m, CH2CH2CH2CH2CH2). 13C NMR (75 MHz CDCl3)δ: 142.57, 140.09, 137.31, 131.81,

128.97, 128.57, 126.78, 121.18, 35.61, 31.45, 29.49, 29.32.

2.9.3. 1,9-Bis(4'-cyanobiphenyl-4-yl)nonane, 32




to this a mixture of a solution of FeCl3 (10.53 g, 0.10 mol), H2O (50 ml) and 32% HCl (35.6 ml)







chromatography using DCM as eluent, R.f. 0.65, before recrystallisation from EtOH to yield

fine yellow crystals. Yield: 2.96 g, 39%. TCrNTB 86 °C, TNTBN 108 °C, TNI 124 °C. Elemental analysis:


Infrared ν cm-1: 2927 (C-H), 2224 (C≡N), 1602, 1493, 1178, 823, 782, 567, 521. 1H NMR (300

MHz CDCl3)δ: 7.74 (4H, d, J 8.5 Hz, Ar), 7.69 (4H, d, J 8.5 Hz, Ar), 7.54 (4H, d, J 8.5 Hz, Ar), 7.32

(4H, d, J 8.5 Hz, Ar), 2.68 (4H, t, J 7.7 Hz, ArCH2CH2), 1.67 (4H, m, ArCH2CH2CH2CH2), 1.35 (10H,

m, CH2CH2CH2CH2CH2). 13C NMR (750 MHz CDCl3)δ: 145.61, 143.77, 136.47, 132.58, 129.19,

127.48, 127.08, 119.05, 110.57, 35.65, 31.41, 29.49, 29.32. MS (ESI+, m/z): [M+Na]+

Calculated for C35H34N2Na: 505.2620 Found: 505.2611.

2.10. 1,11-Bis(4'-cyanobiphenyl-4-yl)undecane, CB11CB

1,11-Bis(4'-cyanobiphenyl-4-yl)undecane, CB11CB was synthesised in the same manner as

compound 23 with the exception of the reduction of the carbonyl, the method for which is

described in 2.7.2.. The acid chloride starting material had to be synthesised from the

required carboxylic acid. Synthetic details for this step are reported. The spectroscopic data

for CB11CB and its intermediates are provided and agree with previously reported data [6].

The synthetic route used to obtain undecandioyl chloride, is shown in scheme 5;


S27

Scheme 5.

2.10.1. Undecandioyl chloride

A solution of undecandioic acid (5.00 g, 0.023 mol) and thionyl chloride (4.2 ml, 0.058 mol)

was heated at 70 °C for 2 h. Excess thionyl chloride was then removed via vacuum distillation

to yield a clear yellow liquid which was used without further purification. Yield: 5.57 g, 99%.

2.10.2. 1,11-Bis(4'-bromobiphenyl-4-carbonyl)nonane, 33


of undecandioyl chloride (5.57 ml, 0.022 mol) and 4-bromobiphenyl (10.71 g, 0.046 mol) in



stirred overnight. The reaction mixture was added to H2O (250 ml) and the white precipitate

collected by vacuum filtration. The crude product thus obtained was recrystallized from EtOAc

and collected as a white solid. Yield: 10.17 g, 73%. TCrI 191 °C. Infrared ν cm-1: 2922 (C-H),

2910 (C-H), 1674 (C=O), 1282, 1085, 1000, 830, 806, 578, 535. 1H NMR (300 MHz CDCl3)δ: 8.05

(4H, d, J 7.8 Hz, Ar), 7.66 (4H, d, J 7.8 Hz, Ar), 7.62 (4H, d, J 7.8 Hz, Ar), 7.51 (4H, d, J 7.8 Hz,

Ar), 3.01 (4H, t, J 7.4 Hz, COCH2CH2), 1.78 (4H, m, COCH2CH2CH2), 1.38 (10H, m, CH2CH2CH2).

Relative insolubility of the compound precluded the possibility of 13C NMR spectroscopy.

2.10.3. 1,11-Bis(4'-bromobiphenyl-4-yl)undecane, 34








EtOAc and collected as a white solid. Yield: 7.02 g, 71%. TCrI 110 °C. Infrared ν cm-1: 2922 (C-


S28

H), 2851 (C-H), 1481, 1389, 1077, 1001, 808, 505. 1H NMR (300 MHz CDCl3)δ: 7.57 (4H, d, J 8.1

Hz, Ar), 7.49 (4H, d, J 8.1 Hz, Ar), 7.46 (4H, d, J 8.1 Hz, Ar), 7.27 (4H, d, J 8.1 Hz, Ar), 2.66 (4H,

t, J 7.7 Hz, ArCH2CH2), 1.66 (4H, quin, J 7.4 Hz, ArCH2CH2CH2CH2), 1.33 (14H, m,


128.57, 126.77, 121.17, 35.62, 31.47, 29.63, 29.57, 29.51, 29.35.

2.10.4. 1,11-Bis(4'-cyanobiphenyl-4-yl)undecane, 35




to this a mixture of a solution of FeCl3 (7.30 g, 0.10 mol), H2O (40 ml) and 32% HCl (24.6 ml)






and washed with copious amounts of H2O. This product was purified by silica gel flash

chromatography using DCM as eluent, R.f. 0.58, before recrystallisation from EtOH to yield

fine yellow crystals. Yield: 2.97 g, 53%. TCrNTB 105 °C, TNTBN 109 °C, TNI 126 °C. Elemental

analysis: Calculated for C37H38N2: C, 87.02%, H, 7.50%, N, 5.49%. Found: C, 87.20%, H, 7.66%,

N, 5.47%. Infrared ν cm-1: 2922 (C-H), 2851 (C-H), 2225 (C≡N), 1603, 1492, 1177, 1004, 851,

812, 565, 539. 1H NMR (300 MHz CDCl3)δ: 7.74 (4H, d, J 8.6 Hz, Ar), 7.69 (4H, d, J 8.6 Hz, Ar),

7.53 (4H, d, J 8.6 Hz, Ar), 7.31 (4H, d, J 8.6 Hz, Ar), 2.68 (4H, t, J 7.7 Hz, ArCH2CH2), 1.67 (4H,

quin, J 7.3 Hz, ArCH2CH2CH2CH2), 1.33 (14H, m, CH2CH2CH2CH2CH2). 13C NMR (75 MHz CDCl3)δ:

145.62, 143.80, 136.47, 132.57, 129.18, 127.47, 127.07, 119.04, 110.57, 35.65, 31.41, 29.64,

29.57, 29.51, 29.33. MS (ESI+, m/z): [M+Na]+ Calculated for C37H38N2Na: 533.2933. Found:

533.2924.

2.11. 1,13-Bis(4'-cyanobiphenyl-4-yl)tridecane, CB13CB

1,13-Bis(4'-cyanobiphenyl-4-yl)tridecane, CB13CB was synthesised in the same manner as

compound 23 with the exception of the reduction of the carbonyl, the method for which is

described in 2.7.2.. The acid chloride starting material had to be synthesised from the


S29

required carboxylic acid. Synthetic details for this step are reported in 2.10.1.. The

spectroscopic data for CB13CB and its intermediates are provided.

2.11.1. Tridecandioyl acid

This compound was synthesised according to the procedure described in 2.10.1. with a

solution of 1,11-undecandicarboxylic acid (10.00 g, 0.04 mol), and thionyl chloride (6.7 ml,

0.09 mol) was heated at 70 °C for 2 h. Excess thionyl chloride were then removed via vacuum

distillation to yield a clear yellow liquid which was used without further purification. Yield:

10.76 g, 95%.

2.11.2. 1,13-Bis(4'-bromobiphenyl-4-carbonyl)undecane, 36


of tridecandioyl chloride (10.76 ml, 0.038 mol) and 4-bromobiphenyl (17.91 g, 0.077 mol) in



stirred overnight. The reaction mixture was added to H2O (250 ml) and the white precipitate

collected by vacuum filtration. The crude product thus obtained was recrystallized from

toluene and collected as an orange solid. Yield: 13.58 g, 53%. TCrI 187 °C. Infrared ν cm-1: 2911

(C-H), 2874 (C-H), 1673 (C=O), 1602, 1373, 1262, 1209, 1084, 998, 814, 772, 461. 1H NMR (300


(4H, d, J 8.5 Hz, Ar), 3.15 (4H, t, J 7.8 Hz, COCH2CH2), 1.79 (4H, m, COCH2CH2CH2), 1.35 (14H,

m, CH2CH2CH2). Relative insolubility of the compound precluded the possibility of 13C NMR

spectroscopy.

2.11.3. 1,13-Bis(4'-bromobiphenyl-4-yl)tridecane, 37








1:1 toluene/EtOH mixture and collected as a white solid. Yield: 7.75 g, 60%. TCrI 109 °C TNI 107


S30

°C. Infrared ν cm-1: 2915 (C-H), 2847 (C-H), 1482, 1082, 1002, 808, 719, 490. 1H NMR (300


(4H, d, J 8.2 Hz, Ar), 2.65 (4H, t, J 7.7 Hz, ArCH2CH2), 1.65 (4H, quin, J 7.4 Hz, ArCH2CH2CH2CH2),

1.30 (18H, m, CH2CH2CH2CH2CH2). 13C NMR (75 MHz CDCl3)δ: 142.62, 140.08, 137.29, 131.81,

128.98, 128.58, 126.78, 121.17, 35.63, 31.52, 29.67, 29.61, 29.54, 29.52, 29.38.

2.11.4. 1,13-Bis(4'-cyanobiphenyl-4-yl)tridecane, 38




to this a mixture of a solution of FeCl3 (14.00 g, 0.20 mol), H2O (75 ml) and 32% HCl (30 ml)






and washed with copious amounts of H2O. This product was purified by silica gel flash

chromatography using DCM as eluent, R.f. 0.50, before recrystallisation from EtOH to yield a

white solid. Yield: 2.92 g, 47%. TCrN 106 °C, TNTBN 105 °C, TNI 122 °C. Elemental analysis:


Infrared ν cm-1: 2920 (C-H), 2849 (C-H), 2225 (C≡N), 1604, 1494, 1177, 819, 786, 562, 521. 1H


Hz, Ar), 7.32 (4H, d, J 8.5 Hz, Ar), 2.68 (4H, t, J 7.7 Hz, ArCH2CH2), 1.67 (4H, m,

ArCH2CH2CH2CH2), 1.32 (18H, m, CH2CH2CH2CH2CH2). 13C NMR (75 MHz CDCl3)δ: 145.62,

143.82, 136.45, 132.58, 129.21, 127.49, 127.09, 119.07, 110.54, 35.66, 31.44, 29.68, 29.62,

29.54, 29.35. MS (ESI+, m/z): [M+Na]+ Calculated for C39H42N2Na: 561.3246. Found: 561.3239.

2.12. Synthesis 1,3-bis(4'-cyanobiphenyl-4-yloxy)propane, CBO3OCB

The synthetic route used to obtain 1,3-bis(4'-cyanobiphenyl-4-yloxy)propane, CBO3OCB, is

shown in scheme 1;


S31

Scheme 6.

2.12.1. 1,3-Bis(4'-cyanobiphenyl-4-yloxy)propane, 39

A mixture of 1,3-dibromopropane (0.8 ml, 0.008 mol), 4-cyano-4'-hydroxybiphenyl (3.26 g,

0.017 mol), potassium carbonate (4.11 g, 0.029 mol) and cyclohexanone (25 ml) was heated

at reflux overnight. The reaction mixture was then cooled to room temperature, poured into

H2O (150 ml) and the brown precipitate that resulted was collected by vacuum filtration. The

crude product obtained was recrystallised from EtOAc to give the title compound as an off

white coloured solid. Yield: 1.51 g, 76%. TCrI 184 °C, TNTBN 83 °C, TNI 166 °C. Elemental analysis:

Calculated for C29H22N2O2: C, 80.91%, H, 5.15%, N, 6.51%. Found: C, 80.40%, H, 5.01%, N,

6.52%. Infrared ν cm-1: 2923 (C-H), 2224 (C≡N), 1604, 1485, 1242, 1179, 995, 828, 812, 567,


d, J 8.6 Hz, Ar), 7.02 (4H, d, J 8.6 Hz, Ar), 4.24 (4H, t, J 5.9 Hz, OCH2CH2), 2.33 (2H, quin, J 5.8

Hz, CH2CH2CH2). 13C NMR (100 MHz CDCl3)δ: 159.43, 145.15, 132.60, 131.63, 128.40, 127.11,

119.11, 115.06, 110.13, 64.42, 29.21. MS (ESI+, m/z): [M+Na]+ Calculated for C29H22N2O2Na:

453.1579. Found: 453.1577.

2.13. Synthesis of 1,4-bis(4'-cyanobiphenyl-4-yloxy)butane, CBO4OCB

1,4-Bis(4'-cyanobiphenyl-4-yloxy)butane, CBO4OCB, was synthesised in the same manner as

compound 39, the spectroscopic data for it and its intermediates are provided and agree with

previously reported data [7].

2.13.1. 1,4-Bis(4'-cyanobiphenyl-4-yloxy)butane, 40


mixture of 1,4-dibromobutane (1.0 ml, 0.0085 mol), 4-cyano-4'-hydroxybiphenyl (3.44 g,





S32

crude product was obtained as an off white coloured solid and recrystallised from EtOAc.

Yield: 1.28 g, 34%. TCrN 208 °C, TNI 247 °C. Elemental analysis: Calculated for C30H24N2O2: C,

81.06%, H, 5.44%, N, 6.30%. Found: C, 80.08%, H, 5.46%, N, 6.21%. Infrared ν cm-1: 2956 (C-

H), 2222 (C≡N), 1602, 1494, 1475, 1291, 1240, 1175, 1051, 999, 819, 803, 563, 530. 1H NMR

(400 MHz CDCl3)δ: 7.69 (4H, d, J 8.7 Hz, Ar), 7.63 (4H, d, J 8.7 Hz, Ar), 7.53 (4H, d, J 8.7 Hz, Ar),

7.00 (4H, d, J 8.7 Hz, Ar), 4.11 (4H, m, OCH2CH2), 2.04 (4H, m, OCH2CH2CH2CH2). 13C NMR (100

MHz CDCl3)δ: 159.58, 145.19, 132.58, 131.50, 128.36, 127.09, 119.07, 115.06, 110.13, 67.59,

25.98. MS (ESI+, m/z): [M+Na]+ Calculated for C30H24N2O2Na: 467.1735. Found: 467.1730.

2.14. Synthesis of 1,5-bis(4'-cyanobiphenyl-4-yloxy)pentane, CBO5OCB

1,5-Bis(4'-cyanobiphenyl-4-yloxy)pentane, CBO5OCB, was synthesised in the same manner as



2.14.1. 1 5-Bis(4'-cyanobiphenyl-4-yloxy)pentane, 41


mixture of 1,5-dibromopentane (1.0 ml, 0.0085 mol), 4-cyano-4'-hydroxybiphenyl (3.33 g,





Yield: 1.50 g, 67%. TCrN 139 °C, TNTBN 79 °C, TNI 187 °C. Elemental analysis: Calculated for

C31H26N2O2: C, 81.20%, H, 5.72%, N, 6.11%. Found: C, 80.31%, H, 5.70%, N, 6.12%. Infrared ν

cm-1: 2943 (C-H), 2219 (C≡N), 1603, 1493, 1472, 1244, 1175, 1032, 1012, 1000, 829, 564, 535.


8.5 Hz, Ar), 7.00 (4H, d, J 8.5 Hz, Ar), 4.06 (4H, t, J 6.3 Hz, OCH2CH2), 1.91 (4H, quin, J 7.0 Hz,

OCH2CH2CH2CH2), 1.71 (2H, quin, J 7.0 Hz, CH2CH2CH2) . 13C NMR (100 MHz CDCl3)δ: 159.65,

145.21, 132.59, 131.39, 128.36, 127.09, 119.14, 115.04, 110.06, 67.87, 28.99, 22.76. MS (ESI+,

m/z): [M+Na]+ Calculated for C31H26N2O2Na: 481.1892. Found: 481.1884.


S33

2.15. Synthesis of 1,7-bis(4'-cyanobiphenyl-4-yloxy)heptane, CBO7OCB

1,7-Bis(4'-cyanobiphenyl-4-yloxy)heptane, CBO7OCB, was synthesised in the same manner as



2.15.1. 1,7-Bis(4'-cyanobiphenyl-4-yloxy)heptane, 42


mixture of 1,7-dibromoheptane (1.4 ml, 0.0085 mol), 4-cyano-4'-hydroxybiphenyl (3.30 g,







H), 2835 (C-H), 2219 C≡N), 1605, 1494, 1479, 1244, 1175, 1034, 820, 564, 531. 1H NMR (400


(4H, d, J 8.8 Hz, Ar), 4.02 (4H, t, J 6.5 Hz, OCH2CH2), 1.84 (4H, quin, J 7.2 Hz, OCH2CH2CH2CH2),

1.52 (6H, m, CH2CH2CH2) . 13C NMR (100 MHz CDCl3)δ: 159.71, 145.22, 132.57, 131.27, 128.33,

127.06, 119.14, 115.03, 110.01, 68.03, 29.16, 29.14, 26.00. MS (ESI+, m/z): [M+Na]+

Calculated for C33H30N2O2Na: 509.2205. Found: 509.2203.

2.16. Synthesis of 1,9-bis(4'-cyanobiphenyl-4-yloxy)nonane, CBO9OCB

1,9-Bis(4'-cyanobiphenyl-4-yloxy)nonane, CBO9OCB, was synthesised in the same manner as



2.16.1. 1,9-Bis(4'-cyanobiphenyl-4-yloxy)nonane, 43


mixture of 1,9-dibromononane (1.7 ml, 0.0085 mol), 4-cyano-4'-hydroxybiphenyl (3.31 g,






S34



H), 2855 (C-H), 2222 (C≡N), 1601, 1494, 1248, 1176, 1033, 824, 813, 563, 532. 1H NMR (400


(4H, d, J 8.7 Hz, Ar), 4.01 (4H, t, J 6.7 Hz, OCH2CH2), 1.82 (4H, quin, J 7.4 Hz, OCH2CH2CH2CH2),

1.49 (4H, m, CH2CH2CH2), 1.39 (6H, m, CH2CH2CH2) . 13C NMR (100 MHz CDCl3)δ: 159.75,

145.23, 132.57, 131.23, 128.32, 127.05, 119.15, 115.04, 109.99, 68.11, 29.49, 29.32, 29.21,

26.03. MS (ESI+, m/z): [M+Na]+ Calculated for C35H34N2O2Na: 537.2518. Found: 537.2515.


S35

Section 3: DSC Traces for CB5OCB

Figure 1 DSC traces obtained for CB5OCB: (a) on cooling after initial heat at 10 °C

min-1 and (b) subsequent reheating.


S36

Section 4: References

[1] Kursanov DN, Parnes ZN, Loim NM. Applications of ionic hydrogenation to organic

synthesis. Synthesis-Stuttgart. 1974(9):633-651.

[2] Paterson DA, Gao M, Kim Y-K, Jamali A, Finley KL, Robles-Hernandez B, Diez-Berart S,

Salud J, de la Fuente MR, Timimi BA, Zimmermann H, Greco C, Ferrarini A, Storey JMD, Lopez

DO, Lavrentovich OD, Luckhurst GR, Imrie CT. Understanding the twist-bend nematic phase:

the characterisation of 1-(4-cyanobiphenyl-4'-yloxy)-6-(4-cyanobiphenyl-4'-yl) hexane

(CB6OCB) and comparison with CB7CB. Soft Matter. 2016;12 6827 - 6840.

[3] Barnes PJ, Douglass AG, Heeks SK, Luckhurst GR. An enhanced odd even effect of

liquid-crystal dimers orientational order in the α,ω-bis(4'-cyanobiphenyl-4-yl)alkanes. Liq

Cryst. 1993;13(4):603-613.

[4] Cestari M, Diez-Berart S, Dunmur DA, Ferrarini A, de la Fuente MR, Jackson DJB, Lopez

DO, Luckhurst GR, Perez-Jubindo MA, Richardson RM, Salud J, Timimi BA, Zimmermann H.

Phase behavior and properties of the liquid-crystal dimer 1 '',7 ''-bis(4-cyanobiphenyl-4 '- yl)

heptane: A twist-bend nematic liquid crystal. Phys Rev E. 2011;84(3):031704.

[5] Tripathi CSP, Losada-Perez P, Glorieux C, Kohlmeier A, Tamba MG, Mehl GH, Leys J.

Nematic-nematic phase transition in the liquid crystal dimer CBC9CB and its mixtures with

5CB: A high-resolution adiabatic scanning calorimetric study. Physical Review E.

2011;84(4):041707.

[6] Mandle RJ, Davis EJ, Archbold CT, Cowling SJ, Goodby JW. Microscopy studies of the

nematic NTB phase of 1,11-di-(1''-cyanobiphenyl-4-yl-undecane. J Mater Chem C.

2014;2(3):556-566.

[7] Emsley JW, Luckhurst GR, Shilstone GN, Sage I. The preparation and properties of the

α,ω-bis(4,4'-cyanobiphenyloxy)alkanes - nematogenic molecules with a flexible core. Mol

Cryst Liq Cryst. 1984;102(8-9):223-233.

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