The chemistry of constrained crown ring systems and fluorescence sensor applications

Abstract

Using anthraquinone as a useful synthetic scaffold and the ability of anthraquinone to form stable intermediate reduction products (i.e. anthrones and anthranols), we have synthesized a wide variety of constrained crown ring systems where the receptor includes several types and patterns of Lewis bases that can tune receptor selectivity for different metal cations. Constrained crown ring systems are defined as macrocycles that contain an intraannular heteroatom, in addition to the normal peripheral Lewis bases that compose the outer ring of the macrocycle. These fluorescence sensors predominantly utilizes the internal charge transfer mechanism to promote fluorescence, but has also led to the development of new photophysical mechanisms, i.e. metal-mediated tautomerization, to selectively detect Zn(II) ion in solution. We are currently pursuing a number of synthetic avenues to incorporate new functional groups and lumophores such that a myiad of different photophysical mechanisms under optimal conditions can be employed to improve solubility, sensitivity and take advantage of the cross pollination of electrochemistry and fluorescence spectroscopy with these sensors which incorporate closely integrated electrochemical, fluorescence and receptor subunits.