Role of MLCT States in the Franck–Condon Region of Neutral, Heteroleptic Cu(I)–4H-imidazolate Complexes: A Spectroscopic and Theoretical StudyClick to copy article linkArticle link copied!
- Carolin MüllerCarolin MüllerInstitute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743 Jena, GermanyLeibniz Institute of Photonic Technology, Albert-Einstein-Straße 9, 07745 Jena, GermanyMore by Carolin Müller
- Martin SchulzMartin SchulzInstitute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743 Jena, GermanyMore by Martin Schulz
- Marc ObstMarc ObstInstitute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743 Jena, GermanyMore by Marc Obst
- Linda ZedlerLinda ZedlerLeibniz Institute of Photonic Technology, Albert-Einstein-Straße 9, 07745 Jena, GermanyMore by Linda Zedler
- Stefanie GräfeStefanie GräfeInstitute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743 Jena, GermanyMore by Stefanie Gräfe
- Stephan Kupfer*Stephan Kupfer*Email: [email protected]Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743 Jena, GermanyMore by Stephan Kupfer
- Benjamin Dietzek*Benjamin Dietzek*Email: [email protected]Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743 Jena, GermanyLeibniz Institute of Photonic Technology, Albert-Einstein-Straße 9, 07745 Jena, GermanyCenter for Energy and Environmental Chemistry Jena (CEEC Jena), Friedrich Schiller University Jena, Lessingstraße 8, 07743 Jena, GermanyMore by Benjamin Dietzek
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.
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