Boronic acid functionalized ferrocene derivatives towards fluoride sensing

Abstract

In this technical report (TR), a robust, readily synthesized molecule with a ferrocene core appended with one or two boronic acid moieties was designed, synthesized, and used toward F- (free fluoride) detection. Through Lewis acid-base interactions, the boronic acid derivatives are capable of binding with F- in an aqueous solution via ligand exchange reaction and is specific to fluoride ion. Fluoride binding to ferrocene causes significant changes in fluorescence or electrochemical responses that can be monitored with field-portable instrumentation at concentrations below the WHO recommended limit. The F- binding interaction was further monitored via proton nuclear magnetic resonance spectroscopy (1H-NMR). In addition, fluorescent spectroscopy of the boronic acid moiety and electrochemical monitoring of the ferrocene moiety will allow detection and estimation of F- concentration precisely in a solution matrix. The current work shows lower detection limit (LOD) of ~15 μM (285 μg/L) which is below the WHO standards. Preliminary computational calculations showed the boronic acid moieties attached to the ferrocene core interacted with the fluoride ion. Also, the ionization diagrams indicate the amides and the boronic acid groups can be ionized forming strong ionic interactions with fluoride ions in addition to hydrogen bonding interactions.