A Photoswitchable Metallocycle Based on Azobenzene: Synthesis, Characterization, and Ultrafast Dynamics

The novel photoswitchable ligand 3,3’‐Azobenz(metPA)2 (1) is used to prepare a [Cu2(1)2](BF4)2 metallocycle (2), whose photoisomerization was characterized using static and time‐resolved spectroscopic methods. Optical studies demonstrate the highly quantitative and reproducible photoinduced cyclic E/Z switching without decay of the complex. Accordingly and best to our knowledge, [Cu2(1)2](BF4)2 constitutes the first reversibly photoswitchable (3d)‐metallocycle based on azobenzene. The photoinduced multiexponential dynamics in the sub‐picosecond to few picosecond time domain of 1 and 2 have been assessed. These ultrafast dynamics as well as the yield of the respective photostationary state (PSSZ = 65 %) resemble the behavior of archetypical azobenzene. Also, the innovative pump‐probe laser technique of gas phase transient photodissociation (τ‐PD) in a mass spectrometric ion trap was used to determine the intrinsic relaxation dynamics for the isolated complex. These results are consistent with the results from femtosecond UV/Vis transient absorption (fs‐TA) in solution, emphasizing the azobenzene‐like dynamics of 2. This unique combination of fs‐TA and τ‐PD enables valuable insights into the prevailing interplay of dynamics and solvation. Both analyses (in solution and gas phase) and quantum chemical calculations reveal a negligible effect of the metal coordination on the switching mechanism and electronic pathway, which suggests a non‐cooperative isomerization process. An azobenzene based Cu(I) metallocycle constituting the prototype for reversibly photoswitchable (3d