CONCLUSION

We present an efficient strategy that exploits dynamic molecular motion in fluid lattices to overcome the geometrical constraints that typically limit TCP in rigid crystalline environments. Employing CS-derived discotic monomers that self-assemble into core-shell helical columnar LCs, we achieve near-quantitative [2 + 2] photocycloaddition within the confined aromatic cores. The reactivity is triggered even in the absence of ideal preorganization: temporary molecular proximity within the fluid LC lattice is sufficient to activate topochemical cycloaddition. The 1D columnar architecture facilitates directional chain growth along the columnar axis, yielding linear helical polymers with well-defined architectures and high structural fidelity. Importantly, the TCP process is dissipative, with the formed polymers undergoing complete depolymerization via cycloreversion, thereby enabling chemical recyclability of the monomers. This reversible polymerization-depolymerization cycle is accompanied by distinct fluorescence color changes, providing a built-in optical readout for real-time monitoring and adding a layer of functional complexity. By integrating this dissipative TCP system into LC films, we further demonstrate proof-of-concept applicability in human-interactive temporary information encryption. Although this study focuses on a specific class of columnar LCs, the underlying design principle—dynamical fluid-lattice-activated TCP—is potentially generalizable to other types of mesophases, offering avenues for further control over polymer dimensionality, sequence, and beyond. Thus, our findings establish a versatile framework for the synthesis of structurally ordered yet functionally tunable polymer materials, advancing the scope of solid-state synthetic methodologies.