Development of Controllable Hetero‐Pauson‐Khand Polymerization to Functional Stimuli‐Responsive Poly(γ‐lactam)s

Abstract Polymers containing lactam structures play a crucial role in both natural biological systems and human life, and their synthesis, functions and applications are of utmost importance for biomimetics and the creation of new materials. In this study, we developed an efficient heterogeneous Pauson–Khand polymerization (h‐PKP) method for the controlled synthesis of main‐chain poly(γ‐lactam)s containing α, β‐unsaturated γ‐lactam functionalities using readily available internal alkynes and imines. The molecular weights of the resulting poly( N −Ts/γ‐lactam)s can be precisely controlled by adjusting the ratio of phenyl formate and nickel. These polymers exhibit high solid‐state luminescence and demonstrate rapid and sensitive dual responsiveness to light and acid stimuli. They further demonstrate strong reactive oxygen species (ROS) generation capability. The unique dual‐emission peaks observed in poly( N −H/γ‐lactam)s obtained through post‐treatment under acidic conditions demonstrate a mechanism of aggregation‐induced intermolecular excited‐state proton transfer specific to lactam structures. The efficient one‐pot synthetic method for poly(γ‐lactam) provides a novel strategy for constructing polymers with γ‐lactam structures in the main chain and the simple and efficient post‐modification method offer a versatile toolbox for functionalizing poly(γ‐lactam)s to expand their potential applications.