Thioureas as Reporting Elements for Metal-Responsive Fluorescent Chemosensors

Proof that sulfur is a viable reporting element for the development of fluorescent chemosensors for metal ions is presented. To date, the majority of metal-responsive fluorescent chemosensors have relied on metal-nitrogen coordination to provide a fluorescence response, most commonly by suppressing photoinduced electron transfer (PET) quenching. While chemosensors with direct application to biology, medicine, and analytical chemistry have been so developed, reliance on the coordination chemistry of nitrogen remains a practical and conceptual limitation. Building on the fact that thioureas can quench fluorescence emission by PET, it is shown that the quenched emission of thiourea-appended naphthalimides can be restored by metal binding and that metal affinity and selectivity can be controlled through structural modification of the thiourea substituents. Further, such chemosensors can function in aqueous media and, unlike nitrogen-based chemosensors, are unresponsive to increases in [H+]. Given that the coordination properties of sulfur are distinct from those of nitrogen, this work lays the foundation for the development of a new class of interesting and useful metal-responsive fluorescent probes.