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Liquid crystal properties of compounds with a variety of polar terminal groups including cyano, fluoro, isothiocyanato, etc., were studied well, however, not enough attention was given to nitro terminal compounds. In this work, a series of fluorine tail terminated alkoxy nitrobiphenyl compounds were synthesised and their mesogenic properties were analysed. In addition, the simple alkoxy nitrobiphenyl compounds were synthesised and analysed in order to compare them with fluoro-alkoxy nitrobiphenyl compounds and for binary mixture analysis. Fluorine tail termination to the alkoxy chain does suppress the smectic phase that was observed for the simple alkoxy nitrobiphenyl compounds with longer chains. Fluorine tail terminated alkoxy nitrobiphenyl compounds with longer chains (C7-C10) show monotropic nematic phase around ambient temperature and supercooling properties and these compounds are useful for a binary mixture analysis. Moreover, computation and experimental analyses of the alkoxy nitrobiphenyl compounds were performed to investigate the potential use of these nitro terminal compounds as chemoresponsive liquid crystal materials. 

The development of responsive soft materials with tailored functional properties based on the chemical reactivity of atomically precise inorganic interfaces has not been widely explored. In this communication, guided by first-principles calculations, we design bimetallic surfaces comprised of atomically thin Pd layers deposited onto Au that anchor nematic liquid crystalline phases of 4′- n -pentyl-4-biphenylcarbonitrile (5CB) and demonstrate that the chemical reactivity of these bimetallic surfaces towards Cl 2 gas can be tuned by specification of the composition of the surface alloy. Specifically, we use underpotential deposition to prepare submonolayer to multilayers of Pd on Au and employ X-ray photoelectron and infrared spectroscopy to validate computational predictions that binding of 5CB depends strongly on the Pd coverage, with ∼0.1 monolayer (ML) of Pd sufficient to cause the liquid crystal (LC) to adopt a perpendicular binding mode. Computed heats of dissociative adsorption of Cl 2 on PdAu alloy surfaces predict displacement of 5CB from these surfaces, a result that is also confirmed by experiments revealing that 1 ppm Cl 2 triggers orientational transitions of 5CB. By decreasing the coverage of Pd on Au from 1.8 ± 0.2 ML to 0.09 ± 0.02 ML, the dynamic response of 5CB to 1 ppm Cl 2 is accelerated 3X. Overall, these results demonstrate the promise of hybrid designs of responsive materials based on atomically precise interfaces formed between hard bimetallic surfaces and soft matter. 

Defects may display high reactivity because the specific arrangement of atoms differs from crystalline surfaces. We demonstrate that high-temperature steam pretreatment of palladium catalysts provides a 12-fold increase in the mass-specific reaction rate for carbon-hydrogen (C–H) activation in methane oxidation compared with conventional pretreatments. Through a combination of experimental and theoretical methods, we demonstrate that an increase in the grain boundary density through crystal twinning is achieved during the steam pretreatment and oxidation and is responsible for the increased reactivity. The grain boundaries are highly stable during reaction and show specific rates at least two orders of magnitude higher than other sites on the palladium on alumina (Pd/Al 2 O 3 ) catalysts. Theoretical calculations show that strain introduced by the defective structure can enhance C–H bond activation. Introduction of grain boundaries through laser ablation led to further rate increases.