Exploring the light-induced dynamics in solvated metallogrid complexes with femtosecond pulses across the electromagnetic spectrum

Maria A Naumova, Aleksandr Kalinko, Joanne W L Wong, Sol Laura Alvarez Gutierrez, Jie Meng, Mingli Liang, Mohamed Abdellah, Huifang Geng, Weihua Lin, Katharina Kubicek, Mykola Biednov, Frederico Lima, Andreas Galler, Peter Zalden, Stefano Checchia, Pierre-Adrien Mante, Jennifer Zimara, Dirk Schwarzer, Serhiy Demeshko, Vadim MurzinDavid Gosztola, Martin Jarenmark, Jianxin Zhang, Matthias Bauer, Max Latevi Lawson Daku, Dmitry Khakhulin, Wojciech Gawelda, Christian Bressler, Franc Meyer, Kaibo Zheng, Sophie E Canton

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Abstract

Oligonuclear complexes of d4-d7 transition metal ion centers that undergo spin-switching have long been developed for their practical role in molecular electronics. Recently, they also have appeared as promising photochemical reactants demonstrating improved stability. However, the lack of knowledge about their photophysical properties in the solution phase compared to mononuclear complexes is currently hampering their inclusion into advanced light-driven reactions. In the present study, the ultrafast photoinduced dynamics in a solvated [2 × 2] iron(II) metallogrid complex are characterized by combining measurements with transient optical-infrared absorption and x-ray emission spectroscopy on the femtosecond time scale. The analysis is supported by density functional theory calculations. The photocycle can be described in terms of intra-site transitions, where the FeII centers in the low-spin state are independently photoexcited. The Franck-Condon state decays via the formation of a vibrationally hot high-spin (HS) state that displays coherent behavior within a few picoseconds and thermalizes within tens of picoseconds to yield a metastable HS state living for several hundreds of nanoseconds. Systematic comparison with the closely related mononuclear complex [Fe(terpy)2]2+ reveals that nuclearity has a profound impact on the photoinduced dynamics. More generally, this work provides guidelines for expanding the integration of oligonuclear complexes into new photoconversion schemes that may be triggered by ultrafast spin-switching.

Original languageEnglish
Article number214301
JournalThe Journal of Chemical Physics
Volume152
Issue number21
ISSN0021-9606
DOIs
Publication statusPublished - 2020

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