"Covalent-Disassembly"-Based Approaches For Sensing Applications

The detection of analytes with small molecular probes is crucial for the analysis and understanding of chemical, medicinal, environmental and biological situations as well as processes. Classic detection approaches rely on the concept of molecular recognition and bond formation reactions. Bond breakage reactions have been less explored in similar contexts. This concept article introduces metal-salen and metal-imine complexes as "covalent-disassembly"-based (DB)-probes for detecting polyoxophosphates, thiols, amino acids, HCN and changes in pH. It discusses the roles, importance and combinations of structurally functionalized molecular building blocks in the construction of DB-probes. Applications of optimized DB-probes for analyte detection in live cells and foodstuff are also discussed. Furthermore, the mechanism of the disassembly of a Fe(III)-salen probe upon pyrophosphate binding is presented. Extraordinary selectivity for this analyte was achieved by a multistep disassembly sequence including an unprecedented structural change of the metal complex (i. e. "induced-fit" principle). Design principles of probes for sensing applications following the "covalent-disassembly" approach are summarized, which will help improving current systems, but will also facilitate the development of new DB-probes for challenging analytic targets.