A Ratiometric Luminescent Switch Based on Platinum Complexes Tethered to a Crown-Ether Scaffold

A ratiometric chemosensor for potassium is reported, based on phosphorescent dinuclear cyclometalated PtII complexes featuring a cis-crown ether as the cation-recognition unit. The metal complexes are blue luminescent in a non-aggregated state but become strongly orange emissive when in a close physical proximity, as is the case when the macrocycle is in the folded state. Upon binding of the cation, unfolding occurs, resulting in a pronounced change in the emission properties (e.g. emission wavelength), which can be used for ratiometric sensing applications. The reversibility of the binding was confirmed by competitive titration experiments with unsubstituted 18-crown-6; the system shows supramolecular switching behavior.