Accurate Prediction of Mössbauer Hyperfine Parameters in Bis-Axially Coordinated Iron(II) Phthalocyanines Using Density Functional Theory Calculations: A Story of a Single Orbital Revealed by Natural Bond Orbital Analysis

Density Functional Theory (DFT) calculations coupled with several exchange-correlation functionals were used for the prediction of Mössbauer hyperfine parameters of 36 bis-axially coordinated iron­(II) phthalocyanine complexes with the general formulas PcFeL₂, PcFeL′L″, and [PcFeX₂]^2–, including four new compounds. Both gas-phase and PCM calculations using BPW91 and MN12L exchange-correlation functionals were found to accurately predict both Mössbauer quadrupole splittings and the correct trends in experimentally observed isomer shifts. In comparison, hybrid exchange-correlation functionals underestimated quadrupole splittings, while still accurately predicted isomer shifts. Out of ∼40 exchange-correlation functionals tested, only MN12L was found to correctly reproduce quadrupole splitting trends in the PcFeL₂ complexes coordinated with phosphorus-donor axial ligands (i.e., P­(OnBu)₃ ≈ P­(OEt)₃ < PMe₃ < P­[(CH₂O)₂CH₂]-p-C₆H₄NO₂ < PEt₃ ≈ PnBu₃). Natural Bond Orbital (NBO) analysis was successfully used to explain the general trends in the observed quadrupole splitting for all compounds of interest. In particular, the general trends in the quadrupole splitting correlate well with the axial ligand dependent, NBO-predicted population of the 3d_z2 orbital of the Fe ion and are reflective of the hypothesis proposed by Ohya and co-workers (Inorg. Chem., 1984, 23, 1303) on the adaptability of the phthalocyanine’s π-system toward Fe-L_ax interactions. The first X-ray crystal structure of a PcFeL₂ complex with axial phosphine ligands is also reported.