Excited-State Kinetics of an Air-Stable Cyclometalated Iron(II) Complex |
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| Authors: | Jakob Steube Dipl-Chem Lukas Burkhardt Ayla Päpcke Johannes Moll Dr Peter Zimmer Dr Roland Schoch Dr Christoph Wölper Prof?Dr Katja Heinze Prof?Dr Stefan Lochbrunner Prof?Dr Matthias Bauer |
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| Institution: | 1. Institute of Inorganic Chemistry and Center for Sustainable, Systems Design (CSSD), University of Paderborn, Warburger Straße 100, 33098 Paderborn, Germany;2. Institute of Physics and Department of Life, Light and Matter, University of Rostock, 18051 Rostock, Germany;3. Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg University, Duesbergweg 10–14, 55128 Mainz, Germany;4. Institute for Inorganic Chemistry and Center for Nanointegration, Duisburg-Essen (Cenide), University of Duisburg-Essen, Universitätsstraße 5-7, 45117 Essen, Germany |
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| Abstract: | The complex class Fe(N^N^C)(N^N^N)]+ with an Earth-abundant metal ion has been repeatedly suggested as a chromophore and potential photosensitizer on the basis of quantum chemical calculations. Synthesis and photophysical properties of the parent complex Fe(pbpy)(tpy)]+ (Hpbpy=6-phenyl-2,2′-bipyridine and tpy=2,2′:6′,2′′-terpyridine) of this new chromophore class are now reported. Ground-state characterization by X-ray diffraction, electrochemistry, spectroelectrochemistry, UV/Vis, and X-ray spectroscopy in combination with DFT calculations proves the high impact of the cyclometalating ligand on the electronic structure. The photophysical properties are significantly improved compared to the prototypical Fe(tpy)2]2+ complex. In particular, the metal-to-ligand absorption extends into the near-IR and the 3MLCT lifetime increases by 5.5, whereas the metal-centered excited triplet state is very short-lived. |
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| Keywords: | iron photochemistry excited-state kinetics transient absorption spectroscopy DFT calculations |
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