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Emergent Anti-Ferroelectric Ordering and the Coupling of Liquid Crystalline and Polar Order
Jordan Hobbs ; Calum J. Gibb ; Richard. J. Mandle arXiv,2404,12271. DOI: 10.48550/arXiv.2404.12271
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Abstract: Polar liquid crystals possess three dimensional orientational order coupled with unidirectional electric polarity, yielding fluid ferroelectrics. Such polar phases are generated by rod-like molecules with large electric dipole moments. 2,5-Disubstituted 1,3-dioxane is commonly employed as a polar motif in said systems, and here we show this to suffer from thermal instability as a consequence of equatorial-trans to axial-trans isomerism at elevated temperatures. We utilise isosteric building blocks as potential replacements for the 1,3- dioxane unit, and in doing so we obtain new examples of fluid ferroelectric systems. For binary mixtures of certain composition, we observe the emergence of a new fluid antiferroelectric phase - a finding not observed for either of the parent molecules. Our study also reveals a critical tipping point for the emergence of polar order in otherwise apolar systems. These results hint at the possibility for uncovering new highly ordered polar LC phases and delineate distinct transition mechanisms in orientational and polar ordering.
Purchased from AmBeed: 121219-03-2 ; 2105-94-4 ; 148893-72-5 ; 773134-12-6
CAS No. : | 121219-03-2 | MDL No. : | MFCD00051907 |
Formula : | C6H4BrFO | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | MRQYTJXVULSNIS-UHFFFAOYSA-N |
M.W : | 191.00 | Pubchem ID : | 2779153 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P305+P351+P338 | UN#: | |
Hazard Statements: | H302-H319 | Packing Group: | |
GHS Pictogram: |
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* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43.5% | With potassium carbonate;1,1 bis(di-tert-butylphosphino)ferrocene palladium dichloride; In N,N-dimethyl-formamide; at 20 - 100℃; for 4h; | Intermediate 43-6: Ethyl 2-f4-f2-fluoro-4-hvdroxyphenyl)cvclohex-3-enyl)acetateA solution of Intermediate 43-7 (18.48 g, 62.82 mmol) in DMF (100 mL) was added to a stirred suspension of 4-bromo-3-fluorophenol (10 g, 52.36 mmol), potassium carbonate (21.71 g, 157.07 mmol) and [l,l-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1.163 g, 1.41 mmol) in DMF (100 mL) at ambient temperature. The resulting suspension was stirred at 80 0C under nitrogen for 2 hours. The reaction was incomplete so the temperature was increased to 100 0C and the reaction mixture was stirred for a further 30 minutes and then further [l,l-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1.163 g, 1.41 mmol) was added and the suspension was stirred at 100 0C for a further 45 minutes and then further [l,l-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (400 mg, 0.487 mmol) was added and the suspension was stirred at 100 0C for a further 45 minutes. The reaction mixture was evaporated to dryness and redissolved in EtOAc (200 mL) and 2M HCl (250 mL) was cautiously added. The aqueous layer was further extracted with EtOAc (3 x 200 mL) and the organic extracts were combined, washed saturated brine (300 mL), dried over MgSO4, filtered and evaporated to afford crude product. The crude <n="133"/>product was purified by flash silica chromatography, elution gradient 0 to 20% EtOAc in isohexane. Pure fractions were evaporated to dryness to afford the title compound (6.34 g, 43.5 %) as a pale yellow oil.1H NMR (400 MHz, CDCl3) δ 1.27 (3H, t), 1.41 - 1.50 (IH, m), 1.85 - 1.95 (2H, m), 2.14 - 2.21 (IH, m), 2.32 (2H, d), 2.32 - 2.48 (3H, m), 4.16 (2H, q), 4.98 (IH, s), 5.81 (IH, s), 6.51 - 6.56 (2H, m), 7.05 - 7.09 (IH, m); m/z 277 (M-H)". |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Synthesis of Intermediate 7A solution of "-butyllithium (2.7N in heptanes; 165 mL, 445 mmol) in THF (300 mL) was cooled to -78°C and treated with 2,2,6,6-tetramethylpiperidine (77 mL, 456 mmol). The reaction mixture was allowed to stir for 30 minutes. A solution of 5-chloro-2- fluoropyridine (50.0 g, 380 mmol) in THF (200 mL) was added drop wise over 30 minutes. After stirring for an additional 30 minutes, the reaction mixture was quenched by bubbling CO2 through the reaction mixture for 10 minutes. The reaction mixture was allowed to warm to RT, and CO2 was bubbled through for an additional 30 minutes. The reaction mixture was then concentrated under reduced pressure and dissolved in DMF (400 mL). 4-Bromo-3-fluorophenol (72.6 g, 380 mmol) was added, followed by potassium carbonate (68.3 g, 494 mmol). The reaction mixture was heated to 120 °C overnight. The reaction mixture was diluted with EtOAc and washed with 4N HC1. The organic layer was separated, washed with water and dried over MgS04. The solvent was removed under reduced pressure. The crude residue was dissolved in Eaton's Reagent (700 mL, 54.0 g, 380 mmol) and the reaction mixture was heated to 120 °C overnight. The reaction mixture was poured onto a mixture of ice and MeOH. The resulting solid was filtered off and washed with water. The solid was suspended in a mixture of MeOH (100 mL) and cyclopropyl methyl ether (200 mL) and filtered off. The grey solid was washed with hexanes and dried yielding 7-bromo-3-chloro-8-fluoro-5H-chromeno[2,3- b]pyridin-5-one (53.76 g, 164 mmol, 43.0 percent yield) as a ~4:1 mixture of isomers. |
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