Bottom‐Up Characterization and Self‐Assembly of Electrogenerated Chemiluminescence Active Ruthenium Nanospheres

Abstract

An approach to electrogenerated chemiluminescence (ECL) signal enhancement, utilizing the highly tailorable ring‐opening metathesis polymerization (ROMP) to generate novel ECL active nanoscale structures is explored. The strategy involves integrating into a single polymer multiple copies of an analogue of the established ECL luminophore, tris(2,2’‐bipyridine)ruthenium(II) (Ru(bpy)32+). Through the addition of hydrophobic and hydrophilic functional groups to the polymer architecture, these ECL active block copolymers are engineered to self‐assemble when exposed to aqueous environments. Self‐assembled ruthenium nanospheres generated through this methodology were found to demonstrate drastic signal amplification properties compared to their non‐assembled polymer counterparts. Characterization methodologies conducted throughout the bottom‐up synthesis of the nanospheres, utilizing the ECL reference of Ru(bpy)32+, facilitated investigating the origins of the nanosphere's signal enhancement.