Coupling the chemical reactivity of bimetallic surfaces to the orientations of liquid crystals

Abstract

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 Cl₂ 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 Cl₂ on PdAu alloy surfaces predict displacement of 5CB from these surfaces, a result that is also confirmed by experiments revealing that 1 ppm Cl₂ 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 Cl₂ 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.