Journal
ACS NANO
Volume 8, Issue 10, Pages 10858-10869Publisher
AMER CHEMICAL SOC
DOI: 10.1021/nn504685t
Keywords
anion recognition; scanning tunneling microscopy; self-assembly; supramolecular chemistry; switching
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Funding
- Indiana University
- Strawn Fellowship
- METACyt Initiative, Indiana University
- Dreyfus Foundation
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Anion-selective (Br- and I-) and voltage-driven crystal switching between two differently packed phases (a reversible arrow beta) was observed in 2D crystalline monolayers of aryl-triazole receptors ordered at solution-graphite interfaces. Addition of Br- and I- was found to stimulate the a reversible arrow beta phase transformation and to produce ion binding to the beta phase assembly, while Cl- and BF4- addition retained the a 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: beta -> a is driven at -1.5 V, while alpha -> beta 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.
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