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

• Published in: The journal of physical chemistry letters Vol. 11; no. 6; pp. 2133 - 2141
• Main Authors: Naumova, Maria A, Kalinko, Aleksandr, Wong, Joanne W. L, Abdellah, Mohamed, Geng, Huifang, Domenichini, Edoardo, Meng, Jie, Gutierrez, Sol Alvarez, Mante, Pierre-Adrien, Lin, Weihua, Zalden, Peter, Galler, Andreas, Lima, Frederico, Kubicek, Katharina, Biednov, Mykola, Britz, Alexander, Checchia, Stefano, Kabanova, Victoria, Wulff, Michael, Zimara, Jennifer, Schwarzer, Dirk, Demeshko, Serhiy, Murzin, Vadim, Gosztola, David, Jarenmark, Martin, Zhang, Jianxin, Bauer, Matthias, Lawson Daku, Max Latevi, Gawelda, Wojciech, Khakhulin, Dmitry, Bressler, Christian, Meyer, Franc, Zheng, Kaibo, Canton, Sophie E
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 19-03-2020
• Subjects: Atom and Molecular Physics and Optics; Atom- och molekylfysik och optik; Chemical Sciences; Fysik; Fysikalisk kemi; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Kemi; light-induced processes; molecular squares; Natural Sciences; Naturvetenskap; photophysics; Physical Chemistry; Physical Sciences; spin-state switching; time-resolved X-ray techniques; ultrafast phenomena
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.9b03883

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.