The strong, non-covalent interactions between π-systems and cations have been the focus of numerous studies on biomolecule structure and catalysis. These interactions, however, have yet to be explored as a sensing mechanism for detecting trace levels of volatile organic compounds (VOCs). In this article, we provide evidence that cation-π interactions can be used to elicit sensitive and selective chemiresistor responses to aromatic VOCs. The chemiresistors are fitted with carboxylate-linked alkali metals bound to the surface of gold monolayer-protected clusters formulated on microfabricated interdigitated electrodes. Sensor responses to aromatic and non-aromatic VOCs are consistent with a model for cation-π interactions arising from association of electron-rich aromatic π-systems to metal ions with the relative strength of attraction following the order K+ > Na+ > Li+. The results point toward cation-π interactions as a promising research avenue to explore for developing aromatic VOC-selective sensors.
Keywords: Alkali metal; BTEX; Carboxylate salt; Pi-interaction; Thiolate ligand.
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