Revealing Hot and Long-Lived Metastable Spin States in the Photoinduced Switching of Solvated Metallogrid Complexes with Femtosecond Optical and X-ray Spectroscopies

Maria A Naumova, Aleksandr Kalinko, Joanne W L Wong, Mohamed Abdellah, Huifang Geng, Edoardo Domenichini, Jie Meng, Sol Laura Gutierrez Alvarez, Pierre-Adrien Mante, Weihua Lin, Peter Zalden, Andreas Galler, Frederico Lima, Katharina Kubicek, Mykola Biednov, Alexander Britz, Stefano Checchia, Victoria Kabanova, Michael Wulff, Jennifer ZimaraDirk Schwarzer, Serhiy Demeshko, Vadim Murzin, David Gosztola, Martin Jarenmark, Jianxin Zhang, Matthias Bauer, Max Latevi Lawson Daku, Wojciech Gawelda, Dmitry Khakhulin, Christian Bressler, Franc Meyer, Kaibo Zheng, Sophie E. Canton*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

An atomistic understanding of the photoinduced spin-state switching (PSS) within polynuclear systems of d4-d7 transition metal ion complexes is required for their rational integration into light-driven reactions of chemical and biological interest. However, in contrast to mononuclear systems, the multidimensional dynamics of the PSS in solvated molecular arrays have not yet been elucidated due to the expected complications associated with the connectivity between the metal centers and the strong interactions with the surroundings. In this work, the PSS in a solvated triiron(II) metallogrid complex is characterized using transient optical absorption and X-ray emission spectroscopies on the femtosecond time scale. The complementary measurements reveal the photoinduced creation of energy-rich (hot) and long-lived quintet states, whose dynamics differ critically from their mononuclear congeners. This finding opens major prospects for developing novel schemes in solution-phase spin chemistry that are driven by the dynamic PSS process in compact oligometallic arrays.
Original languageEnglish
JournalJournal of Physical Chemistry Letters
Volume11
Pages (from-to)2133-2141
ISSN1948-7185
DOIs
Publication statusPublished - 2020

Keywords

  • X-rays
  • Ligands
  • Oscillation
  • Quantum mechanics Kinetics

Cite this

Naumova, M. A., Kalinko, A., Wong, J. W. L., Abdellah, M., Geng, H., Domenichini, E., Meng, J., Gutierrez Alvarez, S. L., Mante, P-A., Lin, W., Zalden, P., Galler, A., Lima, F., Kubicek, K., Biednov, M., Britz, A., Checchia, S., Kabanova, V., Wulff, M., ... Canton, S. E. (2020). Revealing Hot and Long-Lived Metastable Spin States in the Photoinduced Switching of Solvated Metallogrid Complexes with Femtosecond Optical and X-ray Spectroscopies. Journal of Physical Chemistry Letters, 11, 2133-2141. https://doi.org/10.1021/acs.jpclett.9b03883