Photophysics of Anionic Bis(4H-imidazolato)Cu(I) Complexes

in: Chemistry-A European Journal (2022)
Seidler, Bianca; Tran, Jens; Hniopek, Julian; Traber, Philipp; Görls, Helmar; Gräfe, Stefanie; Schmitt, Michael; Popp, Jürgen; Schulz, Martin; Dietzek-Ivanšić, Benjamin
In this paper,the photophysicalbehavior of four panchromatically absorbing, homoleptic bis(4H-imidazo-lato)Cu(I) complexes, with a systematic variation of the electron-withdrawing properties of theimidazolate ligand,werestud-iedby wavelength-dependent time-resolved femtosecond transient absorption spectroscopy. Excitation at400, 480, and 630nmpopulates metal-to-ligand charge-transfer, intra-ligand charge-transferas well as mixed charactersinglet states.The pumpwavelength-dependenttransient absorption data are analyzed by a recently established 2D correlation approach. The data analysis reveals that all excitation conditions yield similar excited state dynamics. Key to the excited-state relaxation is fast,subpicosecond pseudo-Jahn-Teller distortion,which is accompaniedby re-localization of electron densityonto a single ligand from the initially delocalized state atFranck-Condon geometry.The subsequent intersystem crossing to the triplet manifold is followed by a sub-100ps decay to the ground state. The fast,non-radiative decay is rationalized by the low triplet state energy as found by DFT calculations, which suggest the perspective treatment in the strong coupling limit of the energy gap law.

Third party cookies & scripts

This site uses cookies. For optimal performance, smooth social media and promotional use, it is recommended that you agree to third party cookies and scripts. This may involve sharing information about your use of the third-party social media, advertising and analytics website.
For more information, see privacy policy and imprint.
Which cookies & scripts and the associated processing of your personal data do you agree with?

You can change your preferences anytime by visiting privacy policy.