Intercalated Locking Effect Regulates the Dynamic Behavior of Tetraphenylethylene Metal–Organic Frameworks, and Their Thermofluorochromics, NH ₃ Gas Sensing, and Anti‐Counterfeiting

ABSTRACT Two bright blue luminescent Zn(II)‐based MOFs ( Zn‐MOF‐1 and Zn‐MOF‐2 ) were controlledly assembled with two tetraphenylethylene derivatives of different molecular rotor lengths. Molecular rotors arranged in reverse parallel in the structure and freely rotatable result in Zn‐MOF‐1 having significant thermofluorochromics. A large number of uncoordinated saturated Zn(II)‐based SBUs in the Zn‐MOF‐2 structure are obviously exposed inside the pore, providing rich active sites for light‐responsive NH 3 . Zn‐MOF‐2 can quickly and highly sensitive light‐responsive NH 3 molecules within 15 s, with a detection limit (LOD) as low as 0.79 ppm. In addition, Zn‐MOF‐2 simulation was used to detect the exhaled gas environment (10 ppm NH 3 ) in patients with chronic kidney disease (CKD), which proved that it could be used for early detection and prevention of CKD. The single‐crystal structure confirms that NH 3 molecules coordinate with four‐coordinated Zn(II) ions in SBUs, transforming the [D‐A] ∞ into a distinct [D‐A‐D'] ∞ configuration. Based on the differences in thermofluorochromics and light‐responsive NH 3 between the above two examples of Zn(II)‐based MOFs, a complex multi‐level anti‐counterfeiting system was constructed. This work demonstrates the unique advantages of AIEgens containing molecular rotor modules in the controlled construction of framework‐structured artificial intelligent luminescent materials, accelerating the rapid development of smart luminescent sensors.