Halogen Bonding and Hydrogen Bonding Fluorescent Anion Sensing at the Solid-Liquid Interface

Abstract

Halogen bonding (XB) has emerged as a powerful non-covalent interaction in anion supramolecular chemistry and is now well-established for the recognition and sensing of various environmentally and biologically relevant anionic species in solution. To translate the significant potential of XB-mediated anion binding to real-world sensor application requires both a consideration of XB material device integration and utilisation in water; key areas that remain noticeably underdeveloped. Addressing this challenge, we herein report the first example of a XB monolayer architecture for the detection of anions at the solid-liquid interface via fluorescence, enabling sensor re-use and detection of various anions in both organic solvent and in pure water. To this end, a BODIPY-bis(iodo)triazole receptor was covalently immobilized onto glass slides via amide bond formation. Detailed unprecedented comparisons of the anion binding and sensing performance of this XB interface with both an analogous solution-phase XB receptor as well as their hydrogen bonding (HB) congeners revealed that the system’s fluorescence sensing performance is largely retained upon surface immobilization for all tested anions. Interestingly, and in contrast to solution-phase experiments, the XB interface outperformed the HB interface in all cases, both in terms of anion binding strength and signal response. These observations pave the way for a rational translation of established solution-phase fluorescent XB anion receptors to molecular film sensing formats, which, as shown here, both support sensor re-use and circumvent solubility constraints.