Synthesis, Photophysics, Electrochemistry and Electrogenerated Chemiluminescence of PEG-Modified BODIPY dyes in Organic and Aqueous Solutions.

A set polyethylene glycol (PEG) appended BODIPY architectures () have been prepared and studied in CHCl, HO:CHCN (1:1) and aqueous solutions. and both contain a short PEG chain and differ in substitution about the BODIPY framework. is comprised of a fully substituted BODIPY moiety linked to a PEG polymer that is roughly 13 units in length. The photophysics and electrochemical properties of these compounds have been thoroughly characterized in CHCl and aqueous CHCN solutions. The behavior of correlates with established rules of BODIPY stability based on substitution about the BODIPY moiety. ECL for each of these compounds was also monitored. , which is unsubstituted at the 2- and 6-positions dimerized upon electrochemical oxidation while , which contains ethyl groups at the 2- and 6-positions, was much more robust and served as an excellent ECL luminophore. is highly soluble in water due to the long PEG tether and demonstrated modest ECL activity in aqueous solutions using tri-n-propylamine (TPrA) as a coreactant. As such, represents the first BODIPY derivative that has been shown to display ECL in water without the need for an organic cosolvent, and marks an important step in the development of BODIPY based ECL probes for various biosensing applications.