A Motor-Integrated Three-Dimensional Covalent Organic Framework with Dual-Mode Functionality

Biological systems achieve macroscopic functionality through molecular machines operating within precisely organized scaffolds. Replicating this coordinated motion synthetically requires integrating high-performance molecular motors into structurally ordered, yet dynamically active, frameworks. We present a reticular design strategy for incorporating overcrowded alkene rotary motors into 3D covalent organic frameworks (COFs), creating JUC-666 as a prototype. This crystalline material maintains a unidirectional motor rotation in both solution and solid states, as confirmed by spectroscopic and kinetic analyses. The embedded motors enable dual-mode functionality: reversible CO₂ uptake modulation (>83% capacity variation at 273 K) under light-dark cycling, and precisely controlled drug release with light-dosage-proportional kinetics, showing a ∼50-fold increase in cumulative release. These results demonstrate how COFs can bridge molecular-scale motion to macroscopic responses, establishing a platform for designing adaptive functional materials.