Optically Gated Rotary Motion via a Dynamic Ag(I)‐Bridged Molecular Motor–Switch Hybrid

ABSTRACT Dynamic coordination chemistry offers a versatile platform for integrating distinct photoactive units into functional molecular systems. Here, we report a heteroleptic Ag(I) complex, L M –Ag–L D , in which a light‐driven overcrowded‐alkene rotary motor (L M ) and a dithienylethene photoswitch (L D ) are connected through a labile Ag(I) bridge. This well‐defined heteroleptic structure exhibits two key functionalities: wavelength‐selective photochromism and a stepwise bathochromic shift, indicating enhanced electronic communication across the Ag(I) center. Importantly, the thermal helix inversion (THI) half‐life of the motor is modestly yet reproducibly modulated by the isomeric state of L D , providing a proof of concept for optically controlled rotary kinetics. Furthermore, the system shows matrix‐dependent functional decoupling: in a rigid PMMA film, photoisomerization of L D is suppressed, whereas motor rotation remains active. Collectively, these findings establish dynamic coordination as a versatile strategy for constructing optically addressable and environment‐responsive molecular machines with programmable motion control.