Polymerization-Induced Reassembly of Gemini Molecules toward Generating Porous Two-Dimensional Polymers

In situ polymerization of preorganized amphiphilic monomers on various substrates provides a flexible synthetic route to construct high-quality two-dimensional polymers (2DPs) with designed functionalities. However, the detailed polymerization kinetics of these monomers in 2D confinement and their impact on the structural features of 2DPs have not been efficiently explored. Here, using dissipative particle dynamics (DPD) simulations, we unveil the similarity of the polymerization kinetics of the amphiphilic Gemini molecules in both a 2D-confined space and solution and emphasize the key role of the initiator concentration in modifying the morphology of 2DPs. More interestingly, introducing a spacer group into the Gemini monomer facilitates the formation of porous 2DPs. The size and periodic arrangement of pores in these 2DPs could be directly controlled by the Gemini molecular geometries and polymerization kinetics. The insights based on our DPD simulations provide valuable guidelines for the rational design and synthesis of 2DPs from a wider range of amphiphilic molecules.