Switchable Electrostatically Templated Polymerization

We report a switchable, templated polymerization system where the strength of the templating effect can be modulated by solution pH and/or ionic strength. The responsiveness to these cues is incorporated through a dendritic polyamidoamine‐based template of which the charge density depends on pH. The dendrimers act as a template for the polymerization of an oppositely charged monomer, namely sodium styrene sulfonate. We show that the rate of polymerization and maximum achievable monomer conversion are directly related to the charge density of the template, and hence the environmental pH. The polymerization could effectively be switched “ON” and “OFF” on demand, by cycling between acidic and alkaline reaction environments. These findings break ground for a novel concept, namely harnessing co‐assembly of a template and growing polymer chains with tunable association strength to create and control coupled polymerization and self‐assembly pathways of (charged) macromolecular building blocks. A switchable templated polymerization system is reported where the strength of the templating effect can be modulated. Regulating the templating effect enables control over the polymerization kinetics and provides an effective “ON” — “OFF” switch for polymer growth. The controlled co‐assembly of template and growing polymers with modular association strength provides a novel concept to create and control coupled polymerization and self‐assembly pathways.