1.1. General Methods Unless otherwise noted

1.1.

General Methods

Unless otherwise noted, chemical reagents were purchased from commercial suppliers and used without further purification. Solvents were purchased from Fisher Scientific UK and were dried via passage over activated alumina prior to use. Diisopropylamine was distilled immediately prior to use. Spectral data for compounds 3, 6, and 10 was identical to that reported previously,

1-3

whilst compound 7 was prepared as described by us in a

recent publication. 4 Reactions were monitored by thin layer chromatography (TLC) with DCM or hexanes as the eluent. Silica coated aluminium TLC plates used were purchased from Merck (Kieselgel 60 F-254) and visualised using either UV light (254 nm and 365 nm), or by oxidation with either iodine or aqueous potassium permanganate solution. Yields refer to chromatographically (HPLC) and spectroscopically (1H NMR, 13C{1H} NMR) homogenous material. NMR spectra were recorded on a JEOL ECS spectrometer operating at 400 MHz (1H) or 100.5 MHz (13C{1H}) as solutions in CDCl3. Mass spectra were recorded on a Bruker micrOTOF MS-Agilent series 1200LC spectrometer. High-performance liquid chromatography was performed on a Shimadzu Prominence modular HPLC system comprising a LC-20A solvent pump, a DGU-20A5 degasser, a SIL-20A autosampler, a CBM-20A communication bus, a CTO-20A column oven, and a SPO-20A dual wavelength UV-vis detector operating at wavelengths of 230 and 255 nm. Reverse-phase HPLC was performed using an Alltech C18 bonded silica column with a 5 μm pore size, an internal diameter of 4.6 mm and a length of 250 mm, with neat acetonitrile used as the mobile phase. Chromatograms where only one peak was detected are quoted at >99% purity. Elemental analysis data (CHN) were obtained using an Exeter Analytical Inc. CE-440 Analyser and Sartorius S2 analytical balance. Calibration was performed against acetanilide standards and checked by the use of S-benzyl thiouronium chloride as internal standard (analytical grade, Exeter Analytical). Computational chemistry was performed in Gaussian G09 revision e.01, 5with the exception of calculations performed using the PM7 semi-empirical method which were performed in MOPAC2012.

1.2.

Characterisation of Chemical Intermediates

i2:

1,7-bis(4-bromophenyl)hepta-1,6-diyn

A solution of 1,6-heptadiyne (5 g 54 mmol) and 4-iodobromobenzene (28.3 g, 100 mmol) in dry diisopropylamine (300 ml) was thoroughly degassed by sparging with argon whilst vigorously stirring. Once degassed the solution was placed under an atmosphere of dry argon and with vigorous stirring copper chloride (50 mg) and Pd(PPh3)4 (50 mg) were added in one portion. Within one hour the reaction mass became solid, and TLC analysis revealed the consumption of the starting material (Rfhexane ~ 0.2) and the formation of a new material (Rfhexane ~ 0.45). Dichloromethane was added and the suspension filtered to remove precipitated diisopropylammonium iodide. The solvents were removed in vacuo affording a pale yellow oil – this was purified by column chromatography with petroleum ether 40-60 as the eluent, with the chromatographed material recrystalised from hexane affording the title compound as a white solid. Yield:

18.9 g (94 %)

1H

1.88 (2H, quintet, J = 7.0 Hz, Ar-CC-CH2-CH2-CH2-CC-Ar), 2.55 (4H, t, J =

NMR (400 MHz, CDCl3):

7.0 Hz, Ar-CC-CH2-CH2-CH2-CC-Ar), 7.23 (4H, ddd, J = 1.8 Hz, J = 2.2 Hz, J = 8.4 Hz, ArH), 7.40 (4H, ddd, J = 1.8 Hz, J = 2.2 Hz, J = 8.4 Hz, ArH). 13C

NMR (100.5 MHz, CDCl3):

MS (APCI, m/z):

18.83, 27.78, 80.46, 90.48, 121.93, 122.86, 131.59, 133.18 400.955325 (calcd. for C19H15Br2: 400.953501, M + H)

i3:

4,4'-(oxybis(prop-1-yne-3,1-diyl))bis(bromobenzene)

Quantities used: Dipropargylether (10 g, 106 mmol), 4-bromoiodobenzene (62 g, 220 mmol), Pd(PPh3)4 (250 mg), CuCl (250 mg), diisopropylamine (500 ml). The experimental procedure was as described in the synthesis of i10. Column chromatography with 3:1 hexane/DCM as the eluent followed by recrystalisation of the chromatographed material from hexane afforded the title compound as an off white solid. Yield:

36.3 g (95%)

1H

4.49 (4H, s, Ar-CC-CH2-O-CH2-CC-Ar), 7.30 (4H, ddd, J = 1.8 Hz, J = 2.3

NMR (400 MHz, CDCl3):

Hz, J = 8.5 Hz, ArH), 7.44 (4H, ddd, J = 1.8 Hz, J = 2.3 Hz, J = 8.5 Hz, ArH) 13C

NMR (100.5 MHz, CDCl3):

MS (ESI, m/z):

31.06, 85.99, 86.40, 118.90, 122.99, 132.62, 132.81, 402.9331

(calcd. for C18H13Br2O:

402.9328, M + H)

i5:

6-(4-Bromophenyl)hex-5-yn-1-ol

Quantities used: 4-bromo-1-iodobenzene (75.8 g, 0.269 mol), 5-hexyn-1-ol (25 g, 0.255 mol) diisopropylamine (500 ml), copper chloride (100 mg),tetrakistriphenylphosphine palladium (500 mg). The experimental procedure was as described for i2. Column chromatography with a gradient of hexanes/DCM afforded the title compound (RfDCM = 0.4) as a pale yellow oil that crystallised upon standing. Yield:

58.0 g (89%)

1H

1.55 – 1.75 (4H, m, HO-CH2-CH2-CH2-CH2-CC-Ar), 2.18 (1H, Broad S, HO-

NMR (400 MHz, CDCl3):

CH2), 2.39 (2H, t, JHH = 6.7 Hz, -CH2-CH2-CC-Ar), 3.63 (2H, t, JHH = 5.4 Hz, HO-CH2-CH2-), 7.20 (2H, ddd, JHH = 1.8 Hz, JHH = 2.2 Hz, JHH = 8.2 Hz, ArH), 7.35 (2H, ddd, JHH = 1.8 Hz, JHH = 2.2 Hz, JHH = 8.2 Hz, ArH). 13C

NMR (100.5 MHz, CDCl3):

MS (ESI+, m/z):

19.28, 24.96, 31.87, 62.28, 91.30, 121.72, 80.01, 122.90, 131.48, 133.07 253.0217 (calcd. for C12H14BrO: 253.0223, M + H)

i6:

4'-(6-hydroxyhex-1-yn-1-yl)-[1,1'-biphenyl]-4-carbonitrile

A biphasic mixture of 1-(6-hydroxyhex-1-yn-1-yl)-4-bromobenzene (10 mmol, 2.53 g) in THF (50 ml) and 2M aqueous sodium carbonate (50 ml) was degassed by sparging with argon whilst under ultrasonic agitation. After 5 minutes of degassing 4-cyanobenzene boronic acid (11 mmol, 1.62 gg) was added in one portion, the suspension was then heated to 60 °C under reflux with a nitrogen atmosphere before the addition of Pd(PPh3)4 (50 mg) in one portion. TLC analysis of the reaction mixture after 16 h showed consumption of the starting material (RfDCM ~ 0.35) and the presence of a new compound (RfDCM ~ 0.15). The biphasic mixture was cooled to ambient temperature, the aqueous layer was separated washed with DCM (2 x 10 ml) and discarded. The combined organics were dried over magnesium sulphate, concentrated in vacuo and purified by flash chromatography with DCM as the eluent followed by recrystalisation from ethanol/hexanes (1:8) to afford the title compound as a white solid. Yield:

2.5 g (91 %)

1H

1.36 (1H, t, J = 6.0 Hz, HO-CH2-CH2), 1.64 – 1.82 (4H, m, HO-CH2-CH2-CH2-

NMR (400 MHz, CDCl3):

CH2-CC-Ar), 2.48 (2H, t, J = 6.0 Hz, Ar-CC-CH2-CH2), 3.72 (2H, q, J = 6.0 Hz, HO-CH2-CH2-), 7.42 – 7.53 (4H, m, ArH), 7.65 (2H, ddd, J = 1.8 Hz, J = 2.4 Hz, J = 8.5 Hz, ArH), 7.71 (2H, ddd, J = 1.8 Hz, J = 2.4 Hz, J = 8.5 Hz, ArH) 13C{1H}

NMR (100.5 MHz, CDCl3): 19.42, 15.07, 32.01, 62.57, 80.55, 91.86, 111.13, 119.00, 124.55, 127.11, 127.65, 132.35, 132.75, 138.20, 144.99

MS (ESI+, m/z):

276.1383

(calcd. for C19H18NO:

276.1383, M + H)

298.1197

(calcd. for C19H17NNaO:

298.1202, M + Na)

1.3.

Characterisation of Final Compounds

1:

4',4'''-(hepta-1,6-diyne-1,7-diyl)bis(([1,1'-biphenyl]-4-carbonitrile))

Quantities used: 1,7-bis(4-bromophenyl)hepta-1,6-diyne (10 g, 24.9 mmol), THF (200 ml) aqueous sodium carbonate (2M, 100 ml), Pd(PPh3)4 (50 mg). The reaction procedure was as employed of i14. The crude material was purified by flash chromatography with 3:2 hexanes/DCM as the eluent (RfDCM ~ 0.6) followed by recrystalisation from DCM/ethanol to afford the title compound as a low density white solid. Yield:

8.8 g (79 %)

1H

1.94 (2H, quintet, J = 7.0 Hz, Ar-CC-CH2-CH2-CH2-CC-Ar), 2.63 (4H, t, J =

NMR (400 MHz, CDCl3):

7.0 Hz, Ar-CC-CH2-CH2-CH2-CC-Ar), 7.45-7.55 (8H, m, ArH), 7.64 (4H, ddd, J = 1.6 Hz, J = 1.9 Hz, J = 8.4 Hz, ArH), 7.70 (4H, ddd, J = 1.6 Hz, J = 1.9 Hz, J = 8.4 Hz, ArH) 13C

NMR (100.5 MHz, CDCl3):

18.91, 27.92, 80.93, 91.06, 111.19, 118.97, 124.43, 127.14, 127.65, 132.40, 132.77, 138.31, 144.95

MS (ESI+, m/z):

447.184576 (calcd. for C33H23N2:

447.185575, M + H)

469.166421 (calcd. for C33H22N2Na: 469.167519, M + Na) Assay (RP-HPLC):

>99%

Assay (CHN) calcd:

C 88.79%,

H 4.97%

N 6.27%

Assay (CHN) obs:

C 88.81%

H 4.920%

N 6.260%

2:

4',4'''-(oxybis(prop-1-yne-3,1-diyl))bis(([1,1'-biphenyl]-4-carbonitrile))

Quantities used: i11 (1 g, 2.47 mmol) 4-cyanophenyl boronic acid (882 mg, 6 mmol) Pd(PPh3)4 (50 mg) 2M Aq. Na2CO3 (10 ml) THF (20 ml). The experimental procedure was as described in the synthesis of 5. Column chromatography with 7:3 DCM/hexane as the eluent (RfDCM = 0.45) followed by recrystalisation from ethanol afforded the title compound as a white solid. Yield:

0.95 g (86%)

1H

4.57 (4H, s, Ar-CC-CH2-O-CH2-CC-Ar), 7.52 – 7.59 (8H, m, ArH), 7.67 (4H,

NMR (400 MHz, CDCl3):

ddd, J = 1.8 Hz, J = 2.5 Hz, J = 8.4 Hz, ArH), 7.73 (4H, ddd, J = 1.8 Hz, J = 2.5 Hz, J = 8.4 Hz, ArH) 13C

NMR (100.5 MHz, CDCl3):

31.06, 85.99, 86.40, 114.42, 118.90, 122.99, 127.25, 127.74, 132.62, 132.81, 139.26, 144.75

MS (ESI+, m/z):

Assay (RP-HPLC):

449.1652

(calcd. for C32H21N2O:

471.1487

(calcd. for C32H20N2NaO: 471.1468, M + Na)

>99%

449.1648, M + H)

4:

4',4'''-(oxybis(propane-3,1-diyl))bis(([1,1'-biphenyl]-4-carbonitrile))

Compound 2 (100 mg) and Pd/C{En} (2 mg) were suspended in anhydrous THF (3 ml) an the suspension vigorously stirred whilst sparging with hydrogen gas for 0.5 h. The reaction mixture was then filtered through a plug of celite, washing with DCM (5 x 10 ml) and concentrated in vacuo. The solid was redisolved into DCM, the solution was subsequently layered with ethanol and the solvents allowed to diffuse, affording the title compound as a microcrystalline solid. Yield:

84 mg (83%)

1H

1.88 – 1.98 (4H, m, Ar-CH2-CH2-CH2-O-CH2-CH2-CH2-Ar), 2.75 (4H, t, J =

NMR (400 MHz, CDCl3):

7.8 Hz, Ar-CH2-(CH2)2-O-(CH2)2-CH2-Ar), 3.45 (4H, t, J = 6.3 Hz, Ar-(CH2)2CH2-O-CH2-(CH2)2-Ar), 7.30 (4H, ddd, J = 1.8 Hz, J = 2.1 Hz, J = 8.5 Hz, ArH), 7.50 (4H, ddd, J = 1.8 Hz, J = 2.1 Hz, J = 8.5 Hz, ArH), 7.65 (4H, ddd, J = 1.5 Hz, J = 2.0 Hz, J = 8.9 Hz, ArH), 7.70 (4H, ddd, J = 1.5 Hz, J = 2.0 Hz, J = 8.9 Hz, ArH) 13C

NMR (100.5 MHz, CDCl3):

31.31, 32.18, 70.00, 110.67, 119.10, 127.24, 127.56, 129.35, 132.66, 136.74, 142.95, 145.58

MS (ESI+, m/z):

Assay (RP-HPLC):

457.2274

(calcd. for C32H29N2O:

479.2099

(calcd. for C32H28N2NaO: 479.2094, M + Na)

>99%

457.2283, M + H)

5:

4'-((6-(4'-cyano-[1,1'-biphenyl]-4-yl)hex-5-yn-1-yl)oxy)-[1,1'-biphenyl]-4-carbonitrile

Neat DIAD (202 mg, 1 mmol, ≈ 197 μmol) was added dropwise to a solution of i6 (200 mg, 0.72 mmol), 4hydroxy-4′-cyanobiphenyl (156 mg, 0.8 mmol), triphenylphosphine (262 mg, 1 mmol) in anhydrous THF (10 ml) under an atmosphere of dry nitrogen. The reaction was stirred and monitored by TLC until complete consumption of i6 (RfDCM = 0.3) and the accompanying formation of a new spot (RfDCM = 0.65). The reaction mass was concentrated onto Celite and purified by flash chromatography with DCM/hexanes as the eluent. Recrystalisation from ethanol/THF afforded the title compound as a fine white solid. Yield:

305 mg (94 %)

1H

1.79 – 1.90 (2H, m, ArO-CH2-CH2-CH2-CH2-CC-Ar), 1.97 – 2.06 (2H, m,

NMR (400 MHz, CDCl3):

ArO-CH2-CH2-CH2-CH2-CC-Ar), 2.55 (2H, t, J = 7.0 Hz, ArO-CH2-CH2-CH2CH2-CC-Ar), 4.09 (2H, t, J = 7.0 Hz, ArO-CH2-CH2-CH2-CH2-CC-Ar), 7.00 (2H, ddd, J = 2.1 Hz, J = 3.0 Hz, J = 8.4 Hz, ArH), 7.46 – 7.55 (6H, m, [3 overlapping peaks], ArH), 7.60 - 7.74 (8H, m [4 overlapping peaks], ArH) 13C

NMR (100.5 MHz, CDCl3):

28.53, 28.62, 29.09, 67.98, 80.21, 92.07, 110.00, 111.0, 115.04, 118.83, 119.09, 124.53, 126.97, 127.02, 127.46, 128.28, 131.26, 132.21, 132.54, 132.60, 137.98, 144.82, 145.19, 159.72.

MS (ESI+, m/z):

(calcd. for C32H25N2O:

453.1961, M + H)

(calcd. for C32H24N2NaO: 475.1781, M + Na) Assay (RP-HPLC):

>99%

9:

4',4'''-((1E,1'E)-(propane-1,3-diylbis(azanylylidene))bis(methanylylidene))bis(([1,1'-biphenyl]-4-

carbonitrile)) 4-(4-Cyanophenyl)benzaldehyde (414 mg, 2 mmol) in anhydrous methanol (10 ml) was vigorously stirred whilst heating to reflux under an atmosphere of dry nitrogen until complete dissolution of the starting material (~ 5 min). 1,3-Diaminopropane (74 mg, 1 mmol) was added in one portion and the reaction allowed to stir (~ 30 min) whilst maintaining heating under reflux. The precipitate was collected via a hot filtration and recrystallised from ethanol/THF to afford the title compound as a white solid. Yield:

390 mg (86%)

1H

2.15 (2H, quintet, J = 6.7 Hz, Ar-CHN-CH2-CH2-CH2-NHC-Ar), 3.77 (4H, t, J

NMR (400 MHz, CDCl3):

= 6.7 Hz, Ar-CHN-CH2-CH2-CH2-NHC-Ar), 7.63 (4H, d, J = 7.9 Hz, ArH), 7.67 – 7.78 (4H, m, ArH), 7.84 (4H, m, J = 7.9 Hz, ArH), 8.38 (2H, S, Ar-CHN-) 13C

NMR (100.5 MHz, CDCl3):

32.08, 59.44, 111.39, 118.92, 127.55, 127.81, 128.85, 132.75, 136.54, 141.15, 144.91, 160.63

MS (ESI+, m/z):

435.2093

(calcd. for C31H25N4:

453.2074, M + H)

475.1901

(calcd. for C31H24N4Na:

475.1893, M + Na)

Assay (CHN) calcd:

C 82.27 %,

H 5.35% ,

N 12.38%

Assay (CHN) obs:

C 82.21 %

H 5.15%,

N 12.17%

1.4.

Supplemental Phase Diagram/Mixture Data

Figure SI-1:

Plot of TNTB-N versus fraction of CBO5OCB for binary mixtures of CBO5OCB and CB9CB: Fitting with a quadratic function (y = -65.108x^2 + 42.937x+104.14, R2 > 0.95) and evaluation at x = 1 gives a ‘virtual’ (i.e. extrapolated) value of TNTB-N of 82.0 °C.

1.5.

Supplemental Conformational Analysis Data

Figure SI-2:

Histogram plots of the bend-angle probability distributions as determined via the AM1 semiempirical method: compound 3 (a, mean curvature = 103.5 °), compound 4 (b, mean curvature = 91.0 °), compound 5 (c, mean curvature = 100.5 °), compound 6 (d, mean curvature = 104.4 °), compound 7 (e, mean curvature = 95.9 °), compound 8 (f, mean curvature = 108.2 °), compound 9 (g, mean curvature = 115.2 °) and compound 10 (h, mean curvature = 104.5 °).

1.6. 1. 2. 3. 4. 5.

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