Topology‐Tuned Structural Flexibility Toward Customized Piezofluorochromism in Stable Zirconium MOFs

Abstract Albeit serving important roles in high‐techs, the rapid development of crystalline pressure‐responsive materials still heavily relied on the de novo synthesis. Regarding pressure‐responsive metal–organic frameworks (MOFs), their fascinating designability on the metal/ligand component has been extensively utilized, but yet for their network or topology tunability. Derived from the reticular chemistry, we, herein, present a distinctive exploration toward altered piezofluorochromic behaviors of highly‐stable MOFs under GPa‐level, of which is highly topology‐focused. Specifically, each of the three selected organic ligand have yielded its corresponding zirconium‐MOFs under csq ‐ and scu ‐topology, whom all possessed well‐behaved, reversible pressure‐altered photoluminescence (PL). Comprehensive experimental and theoretical investigations revealed that the intrinsic network flexibility of scu ‐topology rendered the MOFs with larger PL response sensitivity, while the relatively rigid csq ‐topology could induce the rarely‐reported pressure‐induced emission enhancement (PIEE). This observed topology‐dependent piezofluorochromism regulation proactively establishes a novel structure‐property relationship in crystalline piezofluorochromic materials, while also spearheads a new horizon for customized smart pressure sensors and optoelectronic devices.