Rostock 2019 – wissenschaftliches Programm
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MO: Fachverband Molekülphysik
MO 6: Metal Complexes
MO 6.5: Vortrag
Montag, 11. März 2019, 15:15–15:30, S HS 001 Biologie
Ultrafast processes in a luminescent mononuclear Cu(I) complex in liquid and solid phase — •Merten Grupe1, Florian Bäppler1, Maximilian Theiß1, Fabian Dietrich2, Stefan Bräse3, Markus Gerhards2, and Rolf Diller1 — 1Dept. of Physics, TU Kaiserslautern, 67663 Kaiserslautern — 2Dept. of Chem., TU Kaiserslautern, 67663 Kaiserslautern — 3Dept. of Org. Chem., KIT, 76131 Karlsruhe
The primary photo induced processes in the OLED-usable mononuclear, heteroleptic Cu(I) complex ([DPEPhos]Cu[PyrTet][1]) were investigated in various solvents and solid state samples via femtosecond (fs) time resolved UV/Vis and fs time resolved mid-IR transient absorption spectroscopy (TA). Vibrational dynamics by mid-IR fs-TA are best described by a tri-exponential fit with τ1 ≈ 0.85 ps, τ2 ≈ 5 ps, τ3 ≈ 37 ps. The UV/Vis data exhibit basically the same dynamics, however, dependent on the solvent a tri- or tetra-exponential fit is required. UV/Vis TA in solid phase leads to a tetra-exponential fit (τ1 ≈ 0.5 ps, τ2 ≈ 2.6 ps, τ3 ≈ 20 ps, τ4 ≈ 200 ps) as well, interestingly, with spectral dynamics significantly differing from that in solution. Based on our results we suggest that flattening distortion and/or a ligand twist (TD-DFT) occur on the time scale of τ2 in solution and that, in contrast to literature on another mononuclear Cu(I) complex[2], ISC (τ3) is not necessarily associated with a spectral blue shift.
[1] Bergmann et al. Chem. Commun., 2013, 49 6501
[2] Iwamura et al. Acc. Chem. Res. 2015, 48 782