29189-60-4Relevant articles and documents
Electronic Structure and Spin Multiplicity of Iron Tetraphenylporphyrins in Their Reduced States as Determined by a Combination of Resonance Raman Spectroscopy and Quantum Chemistry
R?melt, Christina,Ye, Shengfa,Bill, Eckhard,Weyhermüller, Thomas,Van Gastel, Maurice,Neese, Frank
, p. 2141 - 2148 (2018)
Iron tetraphenylporphyrins are prime candidates as catalysts for CO2 reduction. Yet, even after 40 years of research, fundamental questions about the electronic structure of their reduced states remain, in particular as to whether the reducing equivalents are stored at the iron center or at the porphyrin ligand. In this contribution, we address this question by a combination of resonance Raman spectroscopy and quantum chemistry. Analysis of the data allows for an unequivocal identification of the porphyrin as the redox active moiety. Additionally, determination of the spin state of iron is possible by comparing the characteristic shifts of spin and oxidation-state-sensitive marker bands in the Raman spectrum with calculations of planar porphyrin model structures.
Experimental and Theoretical Evidence for an Unusual Almost Triply Degenerate Electronic Ground State of Ferrous Tetraphenylporphyrin
Tarrago, Maxime,R?melt, Christina,Nehrkorn, Joscha,Schnegg, Alexander,Neese, Frank,Bill, Eckhard,Ye, Shengfa
, p. 4966 - 4985 (2021/04/09)
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 [FeII(TPP)] complex (1; TPP2- = tetraphenylporphyrinate dianion) remained highly debated. Specifically, its intermediate-spin (S = 1) ground state was contradictorily assigned to either a nondegenerate 3A2g state with a (dxy)2(dz2)2(dxz,yz)2 configuration or a degenerate 3Egθ state with a (dxy)2(dxz,yz)3(dz2)1/(dz2)2(dxy)1(dxz,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 3A2g and 3Egθ are well-isolated from other triplet states by ca. 4000 cm-1, whereas their splitting ΔA-E is on par with the effective spin-orbit coupling (SOC) constant of iron(II) (≈400 cm-1). Therfore, we invoked an effective Hamiltonian (EH) operating on the nine magnetic sublevels arising from SOC between the 3A2g and 3Egθ states. This approach enabled us to successfully simulate all spectroscopic data of 1 obtained by variable-temperature and variable-field magnetization, applied-field 57Fe M?ssbauer, and terahertz electron paramagnetic resonance measurements. Remarkably, the EH contains only three adjustable parameters, namely, the energy gap without SOC, ΔA-E, an angle θ that describes the mixing of (dxy)2(dxz,yz)3(dz2)1 and (dz2)2(dxy)1(dxz,yz)3 configurations, and the ?rd-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 3A2g (12%), owing to their accidental near-triple degeneracy with ΔA-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.
