Supramolecular chemistry in solution and solid–gas interfaces: synthesis and photophysical properties of monocolor and bicolor fluorescent sensors for barium tagging in neutrinoless double beta decay

Abstract

Translation of photophysical properties of fluorescent sensors from solution to solid–gas environments via functionalized surfaces constitutes a challenge in chemistry. In this work, we report on the chemical synthesis, barium capture ability and photophysical properties of two families of monocolor and bicolor fluorescent sensors. These sensors were prepared to capture barium cations that can be produced in neutrinoless double beta decay of Xe-136. These sensors incorporate crown ether units, two different fluorophores, aliphatic spacers of different lengths, and a silatrane linker that forms covalent bonds with indium tin oxide (ITO) surfaces. Both species shared excellent Ba²⁺ binding abilities. Fluorescent monocolor indicators (FMIs), based on naphthyl fluorophores, showed an off–on character in solution controlled by photoinduced electron transfer. Fluorescent bicolor indicators (FBIs), based on benzo[a]imidazo[5,1,2-cd] fluorophores, exhibited a significant change in their emission spectra on going from the free to the barium-bound state. Both FMIs and FBIs showed similar photophysics in solution and on ITO. However, their performance on ITO was found to be attenuated, but not fully extinguished, with respect to the values obtained in solution, both in terms of intensity and selectivity between the free and Ba²⁺-bound states. Despite this issue, improved performance of the FBIs based on confocal microscopy of the directly attached molecules was observed. These selective FMI and FBI chemosensors installed on tailor-made functionalized surfaces are promising tools to capture the barium cations produced in the double beta decay of Xe-136. The identification of this capture would boost the sensitivity of the experiments searching for the Xe-136-based neutrinoless double beta decay, as backgrounds would be almost totally suppressed.