Electronic Supplementary Information for: The design of smectic liquid crystals with axially chiral biphenyl cores: in search of a proper ferroelectric liquid crystal phase Ziauddin Ahmed, † Carsten Müller, ¶ Marcel Holzwarth, ¶ Christian Haege, ¶ Frank Giesselmann ¶ and Robert P. Lemieux* ,† † Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada ¶ Institute of Physical Chemistry, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany EXPERIMENTAL General. Reactions were performed in oven-dried glassware under an atmosphere of argon unless otherwise stated. 1-Bromo-12,12,14,14,16,16-hexamethyl-12,14,16-trisilaheptadecane and 4,4'-dihydroxy-2,2',6,6'-tetramethyl-3,3'-dinitrobiphenyl (3) were synthesized according to literature procedures and shown to have the expected physical and spectral properties. 1, 2 All reagent grade materials were purchased from Aldrich, TCI America, Combi-Blocks and Alfa Aesar, and used without further purification. Tetrahydrofuran (THF) and dichloromethane (DCM) were dried over 1/16” pellets of 3Å molecular sieves purchased from EMD Millipore and activated at 200 °C in a vacuum oven. 1 H, 13 C and 19 F NMR spectra were acquired in CDCl 3 on a Bruker Avance Spectrometer operating at 300, 75 and 282 MHz respectively. Chemical shifts are reported in units of δ (ppm) relative to residual solvent. Silica gel for chromatography was purchased from Silicycle with an estimated pore size of 60 Å formed from 40-63 mesh (particle size 230-400 µm) silica. Thin layer chromatography was performed on Merck Millipore aluminium plate with 200 µm thick layer of 10-12 µm 60G silica/ with manganese doped zinc silicate (F 254 ) particles. The purity of the final compounds was confirmed by high performance liquid chromatography using a Varian ProStar pump, D-Star Instruments DVW-10 variable wavelength detector and GL Sciences InertSustain HP reverse phase C18 column (250 mm  4.6 mm, 5 µm particles, 100 Å pore size). Chiral resolution was performed on a Chiral Technologies Chiralpak AS column (50 cm x 5 cm, 20 µm particles) with a 9:1 mixture of hexane and ethanol as eluent. High resolution mass spectra were recorded at the Mass Spectrometry Facility at Queens University using a Thermo Fisher Orbitrap Velos Pro with electrospray ionization (ESI). The thermal properties of the final compounds were analyzed by differential scanning calorimetry on a TA Instruments Q2000 instrument. These experiments were performed under nitrogen and the enthalpies measured against an internal reference. Texture analyses were performed on a Nikon Eclipse LV100N POL optical polarizing microscope fitted with a Nikon DS-Ri2 digital camera and Linkam LTS 350 hot stage and TMS 93 temperature controller. Induced optical tilt angles were measured in a rotating analyzer setup previously described in the literature; 3 the linearly polarized light of a He-Ne Laser (λ = 633 nm, Linos Photonics, Göttingen) was circularly polarized with a Glan-Thompson prism and a quarter-wave plate and sent through the sample cells (ITO glass, homogeneous alignment, rubbed nylon and polyimide coating, 1,6 μm cell gap, AWAT1, Poland), which were filled by capillary action in the isotropic phase; the sample temperature was controlled in a brass block with a Julabo FH-25HP thermostat; the analyzer was a second Glan-Thompson prism rotated at a frequency of 3-4 Hz with an Owis HeDL-5540 A02 motor fitted with Hall probes to detect the angular position of the analyzer; the transmitted light intensity was recorded using a Linos Photonics/Spindler & Hoyer 1 Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C. This journal is © The Royal Society of Chemistry 2018