Selective calcium ion sensing with a bichromophoric squaraine foldamer

Several squaraine tethered bichromophoric podand systems 1a-d and a monochromophoric analogue 2 were prepared and characterized. Among these, the bichromophore, 1b, containing five oxygen atoms in the flexible podand moiety was found to specifically bind Ca2+ in the presence of other metal ions such as K+, Na+, and Mg2+. The selective binding of Ca2+ is clear from the absorption and emission spectral changes as well as by the visual color change of 1b from light-blue to an intense purple-blue. Benesi-Hildebrand and Job plots confirmed a 1:1 binding between 1b and Ca2+. Signaling of the binding event is achieved by the cation-induced folding of the bichromophore and the resultant exciton coupling between the squaraine chromophores. The monochromophoric squaraine dye 2 failed to give optical signals upon Ca2+ binding, due to the absence of exciton interaction in the bound complex. Titration of the folded complex 9 with EDTA released the metal ion from the complex, thereby regaining the original absorption and emission properties of the bichromophore. The squaraine foldamer 1b reported here is the first example of a selective chromogenic Ca2+ sensor, which works on the principle of exciton interaction in the folded Ca2+ complex of a bichromophore, the optical properties of which are similar to those of the H-type aggregates of analogous squaraine dyes.