Correlating Valence and 2p3d RIXS Spectroscopies: A Ligand-Field Study of Spin-Crossover Iron(II)

Van Stappen C, Van Kuiken BE, Mörtel M, Ruotsalainen KO, Maganas D, Khusniyarov M, DeBeer S (2024)

Publication Type: Journal article

Publication year: 2024

Journal

Inorganic Chemistry American Chemical Society

DOI: 10.1021/acs.inorgchem.4c00435

Abstract

The molecular spin-crossover phenomenon between high-spin (HS) and low-spin (LS) states is a promising route to next-generation information storage, sensing applications, and molecular spintronics. Spin-crossover complexes also provide a unique opportunity to study the ligand field (LF) properties of a system in both HS and LS states while maintaining the same ligand environment. Presently, we employ complementing valence and core-level spectroscopic methods to probe the electronic excited-state manifolds of the spin-crossover complex [FeII(H2B(pz)2)2phen]0. Light-induced excited spin-state trapping (LIESST) at liquid He temperatures is exploited to characterize magnetic and spectroscopic properties of the photoinduced HS state using SQUID magnetometry and magnetic circular dichroism spectroscopy. In parallel, Fe 2p3d RIXS spectroscopy is employed to examine the ΔS = 0, 1 excited LF states. These experimental studies are combined with state-of-the-art CASSCF/NEVPT2 and CASCI/NEVPT2 calculations characterizing the ground and LF excited states. Analysis of the acquired LF information further supports the notion that the spin-crossover of [FeII(H2B(pz)2)2phen]0 is asymmetric, evidenced by a decrease in eπ in the LS state. The results demonstrate the power of cross-correlating spectroscopic techniques with high and low LF information content to make accurate excited-state assignments, as well as the current capabilities of ab initio theory in interpreting these electronic properties.

Authors with CRIS profile

Max Mörtel Lehrstuhl für Anorganische und Allgemeine Chemie Marat Khusniyarov Department Chemie und Pharmazie

Involved external institutions

Max-Planck-Institut für Chemische Energiekonversion (MPI CEC) / Max-Planck-Institute for Chemical Energy Conversion DE Germany (DE) Synchrotron SOLEIL FR France (FR) Max-Planck-Institut für Kohlenforschung (MPI KoFo) / Max Planck Institute for Coal Research DE Germany (DE)

How to cite

APA:

Van Stappen, C., Van Kuiken, B.E., Mörtel, M., Ruotsalainen, K.O., Maganas, D., Khusniyarov, M., & DeBeer, S. (2024). Correlating Valence and 2p3d RIXS Spectroscopies: A Ligand-Field Study of Spin-Crossover Iron(II). Inorganic Chemistry. https://dx.doi.org/10.1021/acs.inorgchem.4c00435

MLA:

Van Stappen, Casey, et al. "Correlating Valence and 2p3d RIXS Spectroscopies: A Ligand-Field Study of Spin-Crossover Iron(II)." Inorganic Chemistry (2024).

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