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Photoinduced Low-Spin → High-Spin Mechanism of an Octahedral Fe(II) Complex Revealed by Synergistic Spin-Vibronic Dynamics.

ABSTRACT: The Fe(II) low-spin (LS; ¹A_1g, t_2g⁶e_g⁰) → high-spin (HS; ⁵T_2g, t_2g⁴e_g²) light-induced excited spin state trapping (LIESST) mechanism solely involving metal-centered states is revealed by synergistic spin-vibronic dynamics simulations. For the octahedral [Fe(NCH)₆]²⁺ complex, we identify an initial ∼100 fs ¹T_1g → ³T_2g intersystem crossing, controlled by vibronic coupling to antisymmetric Fe-N stretching motion. Subsequently, population branching into ³T_1g, ⁵T_2g (HS), and ¹A_1g (LS) is observed on a subpicosecond time scale, with the dynamics dominated by coherent Fe-N breathing wavepackets. These findings are consistent with ultrafast experiments, methodologically establish a new state of the art, and will give a strong impetus for further intriguing dynamical studies on LS → HS photoswitching.

SUBMITTER: Papai M

PROVIDER: S-EPMC8456406 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature

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Photoinduced Low-Spin → High-Spin Mechanism of an Octahedral Fe(II) Complex Revealed by Synergistic Spin-Vibronic Dynamics.

Pápai Mátyás M

Inorganic chemistry 20210909 18

The Fe(II) low-spin (LS; 1A1g, t2g6eg0) → high-spin (HS; 5T2g, t2g4eg2) light-induced excited spin state trapping (LIESST) mechanism solely involving metal-centered states is revealed by synergistic spin-vibronic dynamics simulations. For the octahedral [Fe(NCH)6]2+ complex, we identify an initial ∼100 fs 1T1g → 3</su ...[more]

PMID: 34498843

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Project description:Four-coordinate transition-metal complexes can adopt a diverse array of coordination geometries, with square planar and tetrahedral coordination being the most prevalent. Previously, we reported the synthesis of a trinuclear Fe(II) complex, Fe3TPM2, supported by a 3-fold-symmetric 2-pyridylpyrrolide ligand [i.e., tris(5-(pyridin-2-yl)-1H-pyrrol-2-yl)methane] that featured a rare cis-divacant octahedral (CDO) geometry at each Fe(II) center. Here, a series of truncated 2-pyridylpyrrolide ligands are described that support mono- and binuclear Fe(II) complexes that also exhibit CDO geometries. Metalation of the tetradentate ligand bis[5-(pyridin-2-yl)-1H-pyrrol-2-yl]methane (H2BPM) in tetrahydrofuran (THF) results in the binuclear complex Fe2(BPM)2(THF)2 in which both Fe(II) ions are octahedrally coordinated. The coordinated THF solvent ligands are labile: THF dissociation leads to Fe2(BPM)2, which features five-coordinate Fe(II) ions. The Fe-Fe distance in these binuclear complexes can be elongated by ligand methylation. Metalation of bis[5-(6-methylpyridin-2-yl)-1H-pyrrol-2-yl]methane (H2BPMMe) in THF leads to the formation of four-coordinate, CDO Fe(II) centers in Fe(BPMMe)2. Further ligand truncation affords bidentate ligands 2-(1H-pyrrol-2-yl)pyridine (PyrPyrrH) and 2-methyl-6-(1H-pyrrol-2-yl)pyridine (PyrMePyrrH). Metalation of these ligands in THF affords six-coordinate complexes Fe(PyrPyrr)2(THF)2 and Fe(PyrMePyrr)2(THF)2. Dissociation of labile solvent ligands provides access to four-coordinate Fe(II) complexes. Ligand disproportionation at Fe(PyrPyrr)2 results in the formation of Fe(PyrPyrr)3 and Fe(0). Ligand methylation suppresses this disproportionation and enables isolation of Fe(PyrMePyrr)2, which is rigorously CDO. Complete ligand truncation, by separating the 2-pyridylpyrrolide ligands into the constituent monodentate pyridyl and pyrrolide donors, affords Fe(Pyr)2(Pyrr)2 in which Fe(II) is tetrahedrally coordinated. Computational analysis indicates that the potential energy surface that dictates the coordination geometry in this family of four-coordinate complexes is fairly flat in the vicinity of CDO coordination. These synthetic studies provide the structural basis to explore the implications of CDO geometry on Fe-catalyzed reactions.

Dataset Information

Photoinduced Low-Spin → High-Spin Mechanism of an Octahedral Fe(II) Complex Revealed by Synergistic Spin-Vibronic Dynamics.

Publications

Photoinduced Low-Spin → High-Spin Mechanism of an Octahedral Fe(II) Complex Revealed by Synergistic Spin-Vibronic Dynamics.

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