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

Autor: Petrikat RI; Fachbereich Chemie, RPTU Kaiserslautern-Landau, Erwin-Schrödinger-Straße 52-54, 67663, Kaiserslautern, Germany., Hornbogen J; Fachbereich Physik, RPTU Kaiserslautern-Landau, Erwin-Schrödinger-Straße 46, 67663, Kaiserslautern, Germany., Schmitt MJP; Fachbereich Chemie, RPTU Kaiserslautern-Landau, Erwin-Schrödinger-Straße 52-54, 67663, Kaiserslautern, Germany., Resmann E; Fachbereich Physik, RPTU Kaiserslautern-Landau, Erwin-Schrödinger-Straße 46, 67663, Kaiserslautern, Germany., Wiedemann C; Fachbereich Chemie, RPTU Kaiserslautern-Landau, Erwin-Schrödinger-Straße 52-54, 67663, Kaiserslautern, Germany., Dilmen NI; Fachbereich Chemie, RPTU Kaiserslautern-Landau, Erwin-Schrödinger-Straße 52-54, 67663, Kaiserslautern, Germany., Schneider H; Fachbereich Chemie, RPTU Kaiserslautern-Landau, Erwin-Schrödinger-Straße 52-54, 67663, Kaiserslautern, Germany., Pick AM; Fachbereich Chemie, RPTU Kaiserslautern-Landau, Erwin-Schrödinger-Straße 52-54, 67663, Kaiserslautern, Germany., Riehn C; Fachbereich Chemie, RPTU Kaiserslautern-Landau, Erwin-Schrödinger-Straße 52-54, 67663, Kaiserslautern, Germany.; Research Center OPTIMAS, RPTU Kaiserslautern-Landau, Erwin-Schrödinger-Straße 46, 67663, Kaiserslautern, Germany., Diller R; Fachbereich Physik, RPTU Kaiserslautern-Landau, Erwin-Schrödinger-Straße 46, 67663, Kaiserslautern, Germany., Becker S; Fachbereich Chemie, RPTU Kaiserslautern-Landau, Erwin-Schrödinger-Straße 52-54, 67663, Kaiserslautern, Germany.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 May 28; Vol. 30 (30), pp. e202400205. Date of Electronic Publication: 2024 Apr 17.
DOI: 10.1002/chem.202400205
Abstrakt: The novel photoswitchable ligand 3,3'-Azobenz(metPA) 2 (1) is used to prepare a [Cu 2 (1) 2 ](BF 4 ) 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, [Cu 2 (1) 2 ](BF 4 ) 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 (PSS Z = 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.
(© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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