Vertical Step-Growth Polymerization Driven by Electrochemical Stimuli from Electrode.

We presented here that vertical step-growth polymerization of monomer A-B via individual A-A or B-B coupling driven by electrochemically switching positive and negative bias on self-assembled A or B electrode. In particular, monomer is Ru(II)(bda)AB (bda = 2,2'-bipyridine-6,6'-dicarboxylate), where A and B are pyridines with pendant carbazolyl and vinyl, which can be dimerized at oxidative potential (ca. 1.0 V vs. Ag/Ag+) and reductive potential (ca. -1.8 V), respectively. Self-assembled monolayers on ITO glass are Ru(II)(bda)PA or Ru(II)(bda)PB (P = pyridine with pendant phosphonic acid). This well-controlled polymerization allows us to synthesize surface confined molecular wire in single molecule precision on electrode with sequence- and topology-controlled possibility. The electrocatalytic performance based on water oxidation of vertically orientated molecular wires rises up with increasing molecular length, and oversteps those of both self-assembled monolayer and randomly electropolymerized film, which were generally studied as two typical models by most of researchers. With function-tuning ability and rapid fabrication, it is highly anticipated that this polymerization and one-pot single molecule controlled assembly has highly promising potentials for practical applications with expectably superior performances.
PMID: 30298609 [PubMed - as supplied by publisher]

Source: Angewandte Chemie - October 8, 2018 Category: Chemistry Authors: Zhang J, Du J, Wang J, Wang Y, Wei C, Li M Tags: Angew Chem Int Ed Engl Source Type: research