Wireless Synthesis and Activation of Electrochemiluminescent Thermoresponsive Janus Objects Using Bipolar Electrochemistry

In this work, bipolar electrochemistry (BPE) is used as a dual wireless tool to generate and to activate a thermoresponsive electrochemiluminescent (ECL) Janus object. For the first time, BPE allows regioselective growth of a poly­(<i>N</i>-isopropylacrylamide) (pNIPAM) hydrogel film on one side of a carbon fiber. It is achieved thanks to the local reduction of persulfate ions, which initiate radical polymerization of NIPAM. By controlling the electric field and the time of the bipolar electrochemical reactions, we are able to control the length and the thickness of the deposit. The resulting pNIPAM film is found to be swollen in water at room temperature and collapsed when heated above 32 °C. We further incorporated a covalently attached ruthenium complex luminophore, Ru­(bpy)<sub>3</sub><sup>2+</sup>, in the hydrogel film. In the second time, BPE is used to activate remotely the electrogenerated chemiluminescence (ECL) of the Ru­(bpy)<sub>3</sub><sup>2+</sup> moieties in the film. We take advantage of the film responsiveness to amplify the ECL signal. Upon collapse of the film, the ECL signal, which is sensitive to the distance between adjacent Ru­(bpy)<sub>3</sub><sup>2+</sup> centers, is strongly amplified. It is therefore shown that BPE is a versatile tool to generate highly sophisticated materials based on responsive polymers, which could lead to sensitive sensors.