Multidimensional Decryption of Metallopolymer at Single-Chain Level

Decrypting information from polymer chains is crucial in investigating molecular data storage media. However, decoding structural information about polymers at the single-chain level remains a significant challenge. Here, we design and construct tetraphenylethylene-based metallopolymers through covalent polymerization followed by intramolecular coordination. The tetratopic monomer as a mixture of Z/E-isomers contains two terminal alkynyl groups for polymerization and two 2,2′:6′,2′′-terpyridine moieties for coordination with Zn(II) or Fe(II) ions. Through incorporating coordination junctions into the polymer backbone, we are able to directly visualize individual metallopolymer chains using scanning tunneling microscopy and obtain multidimensional structural details of metallopolymers, including polymerization degree, Z/E configuration ratio, and the exact configuration sequence of a single polymer. Furthermore, we deduce the relationship between the conformation and corresponding persistence length of metallopolymer chains based on the distribution of bright lobes of coordination junctions in each polymer chain. As such, this study offers an alternative approach to obtaining multidimensional structural information at the single-chain level.