SAMOP 2023 – wissenschaftliches Programm
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MO: Fachverband Molekülphysik
MO 6: Poster I
MO 6.22: Poster
Dienstag, 7. März 2023, 16:30–19:00, Empore Lichthof
Ultrafast dynamics and reversible switching of azobenzene-copper complexes — •Marcel J. P. Schmitt1, Justin Hornbogen2, Raphael I. Petrikat1, Sabine Becker1, Rolf Diller2, and Christoph Riehn1,3 — 1Dept. of Chemistry, RPTU Kaiserslautern — 2Dept. of Physics, RPTU Kaiserslautern — 3Forschungszentrum OPTIMAS, 67663 Kaiserslautern (Germany)
Azobenzenes and their derivatives are known for their reversible E-Z-photoisomerization around the N=N bond.[1,2] Their usage as photoswitchable ligands in metal complexation has also been explored.[3] We present preliminary spectroscopic and ultrafast dynamic results in solution and gas phase of a newly synthesized cyclic [Cu2L2]2+ complex, comprised of two pyridyl-substituted azobenzene ligands (L) in conjunction with Cu(I). We focus on the photoswitching dynamics and possible cooperative effects involving the ligands and metal cores. Therefore, we have examined the dynamics in parallel in solution by transient absorption and in gas phase by femtosecond transient photodissociation using an electrospray ionization mass spectrometer. The resulting ultrafast dynamic spectra reveal multiexponential electronic decay with lifetimes in the sub-ps and ps time ranges for both E and Z configurations. For comparison with UV/Vis and mIR spectra, the binding situation of the copper centers (tetrahedral vs. planar) in the (E,E), (E,Z) and (Z,Z) complexes was quantum chemically modelled by RI-DFT/TD-DFT calculations.
[1] Nat. Rev. Chem. 2019, 3, 133. [2] Chem. Soc. Rev. 2012, 41, 18091825. [3] J. Phys. Chem. Lett. 2019, 10, 6048.