Spiro-Directed Hierarchical Dynamic Covalent Assembly: From Molecular Configuration to Adaptive Porous Networks.

Hierarchical control over both the molecular configuration and supramolecular architecture in radical-based dynamic covalent systems remains challenging. Herein, we designed rigid spiro scaffolds fused with flexible diarylethene units as coupling linkers to regulate the assembly of dicyanomethyl radicals. Spiro congestion enforces the formation of trans-configured dispiromacrocycles and further drives their intermolecular assembly into porous networks, which exhibit reversible mechano- and thermochromic behaviors. This work provides a versatile platform for constructing smart, adaptive porous architectures.