The controlled synthesis of monodisperse, redox-active metallopolymers and their redox properties and functions, including robust electrode derivatization and sensing, remains a challenge. Here a series of polynorbornene homopolymers and block copolymers containing side-chain amidoferrocenyl groups and tetraethylene glycol linkers were prepared via living ring-opening metathesis polymerization initiated by Grubbs’ third-generation catalyst (1). Their molecular weights were determined using MALDI-TOF mass spectra, size exclusion chromatography (SEC), end-group analysis, and the empirical Bard–Anson electrochemical equation. All polymerizations followed a living and controlled manner, and the number of amidoferrocenyl units varied from 5 to 332. These homopolymers and block copolymers were successfully used to prepare modified Pt electrodes that showed excellent stability. The modified Pt electrodes show excellent qualitative sensing of ATP2– anions, in particular those prepared with the block copolymers. The quantitative recognition and titration of [n-Bu4N]2[ATP] was carried out using the CH2Cl2 solution of the homopolymers, showing that two amidoferrocenyl groups of the homopolymers interacted with each ATP2– molecule. This stoichiometry led us to propose the H-bonding modes in the supramolecular polymeric network.

Multi-block polymers are highly desirable for their addressable functions that are both unique and complementary among the blocks. With metal-containing polymers, the goal is even more challenging insofar as the metal properties may considerably extend the materials functions to sensing, catalysis, interaction with metal nanoparticles, and electro- or photochrome switching. Ring-opening metathesis polymerization (ROMP) has become available for the formation of living polymers using highly efficient initiators such as the 3rd generation Grubbs catalyst [RuCl (NHC)(=CHPh)(3-Br-C H N) ], 1. Among the 24 possibilities to introduce 4 blocks of metallopolymers into a tetrablock metallocopolymer by ROMP using the catalyst 1, two viable pathways are disclosed. The synthesis, characterization, electrochemistry, electron-transfer chemistry, and remarkable electrochromic properties of these new nanomaterials are presented.