Aromatic cation−π-dominated pathway control in living supramolecular polymerization

Living supramolecular polymerization (LSP) has attracted widespread attention as a synthetic method for precisely controlling the supramolecular polymerization process and structure. However, effectively coupling the kinetic and thermodynamic energy landscape in LSP to achieve precise control of the polymerization process remains challenging due to the complexity of the multiple energy landscapes involved in the kinetic supramolecular polymerization process. Here we propose a cation−π-dominated pathway regulation strategy that establishes an integrated energy landscape between kinetic traps and thermodynamic polymerization processes by dynamically switching various aromatic cation−π bonding modes, complemented by the photoregulated conformational transformation of azobenzene. By controlling the folding of the azobenzene core conformation under light irradiation, metastable dormant monomers stabilized by individual intramolecular cation−π bonding are competitively formed, which spontaneously transform into thermodynamically favourable ordered two-dimensional nanosheets upon conformational unfolding through alternating intermolecular cation−π interactions. This coupled transition from the kinetic to the thermodynamic pathway can be accelerated by seeds addition, enabling controllable LSP. (Figure presented.).