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Abstract

Iron porphyrins exhibit unrivalled catalytic activity for electrochemical CO₂-to-CO conversion. Despite intensive experimental and computational studies in the last 4 decades, the exact nature of the prototypical square-planar [Fe^II(TPP)] complex (1; TPP^2– = tetraphenylporphyrinate dianion) remained highly debated. Specifically, its intermediate-spin (S = 1) ground state was contradictorily assigned to either a nondegenerate ³A_2g state with a (d_xy)²(d_z²)²(d_xz,yz)² configuration or a degenerate ³E_g^θ state with a (d_xy)²(d_xz,yz)³(d_z²)¹/(d_z²)²(d_xy)¹(d_xz,yz)³ configuration. To address this question, we present herein a comprehensive, spectroscopy-based theoretical and experimental electronic-structure investigation on complex 1. Highly correlated wave-function-based computations predicted that ³A_2g and ³E_g^θ are well-isolated from other triplet states by ca. 4000 cm^–1, whereas their splitting Δ_A–E is on par with the effective spin–orbit coupling (SOC) constant of iron(II) (≈400 cm^–1). Therefore, we invoked an effective Hamiltonian (EH) operating on the nine magnetic sublevels arising from SOC between the ³A_2g and ³E_g^θ states. This approach enabled us to successfully simulate all spectroscopic data of 1 obtained by variable-temperature and variable-field magnetization, applied-field ⁵⁷Fe Mössbauer, and terahertz electron paramagnetic resonance measurements. Remarkably, the EH contains only three adjustable parameters, namely, the energy gap without SOC, Δ_A–E, an angle θ that describes the mixing of (d_xy)²(d_xz,yz)³(d_z²)¹ and (d_z²)²(d_xy)¹(d_xz,yz)³ configurations, and the ⟨r_d^–3⟩ expectation value of the iron d orbitals that is necessary to estimate the ⁵⁷Fe magnetic hyperfine coupling tensor. The EH simulations revealed that the triplet ground state of 1 is genuinely multiconfigurational with substantial parentages of both ³A_2g (<88%) and ³E_g (>12%), owing to their accidental near-triple degeneracy with Δ_A–E = +950 cm^–1. As a consequence of this peculiar electronic structure, 1 exhibits a huge effective magnetic moment (4.2 μB at 300 K), large temperature-independent paramagnetism, a large and positive axial zero-field splitting, strong easy-plane magnetization (g_⊥ ≈ 3 and g_∥ ≈ 1.7) and a large and positive internal field at the ⁵⁷Fe nucleus aligned in the xy plane. Further in-depth analyses suggested that g_⊥ ≫ g_∥ is a general spectroscopic signature of near-triple orbital degeneracy with more than half-filled pseudodegenerate orbital sets. Implications of the unusual electronic structure of 1 for CO₂ reduction are discussed.