Selective Anion-Induced Crystal Switching and Binding in Surface Monolayers Modulated by Electric Fields from Scanning Probes

Anion-selective (Br<sup>–</sup> and I<sup>–</sup>) and voltage-driven crystal switching between two differently packed phases (α ⇆ β) was observed in 2D crystalline monolayers of aryl-triazole receptors ordered at solution–graphite interfaces. Addition of Br<sup>–</sup> and I<sup>–</sup> was found to stimulate the α → β phase transformation and to produce ion binding to the β phase assembly, while Cl<sup>–</sup> and BF<sub>4</sub><sup>–</sup> addition retained the α phase. Unlike all other surface assemblies of either charged molecules or ion-templated 2D crystallization of metal-ligand or receptor-based adsorbates, the polarity of the electric field between the localized scanning tip and the graphite substrate was found to correlate with phase switching: β → α is driven at −1.5 V, while α → β occurs at +1.1 V. Ion-pairing between the countercations and the guest anions was also observed. These observations are supported by control studies including variation of anion species, relative anion concentration, surface temperature, tip voltage, and scanning time.