Role of MLCT States in the Franck-Condon Region of Neutral, Heteroleptic Cu(I)-4 H-imidazolate Complexes: A Spectroscopic and Theoretical Study

Müller C, Schulz M, Obst M, Zedler L, Gräfe S, Kupfer S, Dietzek B (2020)

Publication Type: Journal article

Publication year: 2020

Journal

Journal of Physical Chemistry A American Chemical Society

Book Volume: 124

Pages Range: 6607-6616

Journal Issue: 33

DOI: 10.1021/acs.jpca.0c04351

Abstract

The impact of the electronic structure of a series of 4H-imidazolate ligands in neutral, heteroleptic Cu(I) complexes is investigated. Remarkable broad and strong ligand-dependent absorption in the visible range of the electromagnetic spectrum renders the studied complexes promising photosensitizers for photocatalytic applications. The electronic structure of the Cu(I) complexes and the localization of photoexcited states in the Franck-Condon region are unraveled by means of UV-vis absorption and resonance Raman (rR) spectroscopy supported by time-dependent density functional theory (TD-DFT) calculations. The visible absorption bands stem from a superposition of bright metal-to-ligand charge-transfer (MLCT) and π-π∗ as well as weakly absorbing MLCT states. Additionally, the analysis of involved molecular orbitals and rR spectra upon excitation of MLCT and π-π∗ states highlights the impact of the electronic structure of the 4H-imidazolate ligands on the properties of the corresponding Cu(I) complexes to avail a toolbox for predictive studies and efficient complex design.

Authors with CRIS profile

Carolin Müller

Involved external institutions

Friedrich-Schiller-Universität Jena DE Germany (DE) Leibniz-Institut für Photonische Technologien e.V. DE Germany (DE)

How to cite

APA:

Müller, C., Schulz, M., Obst, M., Zedler, L., Gräfe, S., Kupfer, S., & Dietzek, B. (2020). Role of MLCT States in the Franck-Condon Region of Neutral, Heteroleptic Cu(I)-4 H-imidazolate Complexes: A Spectroscopic and Theoretical Study. Journal of Physical Chemistry A, 124(33), 6607-6616. https://doi.org/10.1021/acs.jpca.0c04351

MLA:

Müller, Carolin, et al. "Role of MLCT States in the Franck-Condon Region of Neutral, Heteroleptic Cu(I)-4 H-imidazolate Complexes: A Spectroscopic and Theoretical Study." Journal of Physical Chemistry A 124.33 (2020): 6607-6616.

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