Spin-Resolved Band Structure of Hoffman Clathrate [Fe(pz)₂Pt(CN)₄] as an Essential Tool to Predict Optical Spectra of Metal–Organic Frameworks

Abstract

Paramount spin-crossover properties of the 3D-Hoffman metalorganic framework (MOF) [Fe(pz)2Pt(CN)4] are generally described on the basis of the ligand field theory, which provides adequate insight into theoretical and simulation analysis of spintronic complexes. However, the ligand field approximation does not take into account the 3D periodicity of the actual complex lattice and surface effects and therefore cannot predict a full-scale periodic structure without utilizing more advanced methods. Therefore, in this paper, the electronic properties of the exemplar MOF were analyzed from the band structure perspective in low-spin (LS) and high-spin (HS) states. The density-of-states spectra determined for both spin-up and spin-down electrons of Fe d6 orbitals indicate spin–orbital splitting and delocalization for HS due to spin polarization in the iron atom ligand field. Presence of the surface states in the real crystal causes a red shift of the metal–metal charge transfer (MMCT) and metal–ligand charge transfer (MLCT) peaks for both HS and LS states. The addition of residual water molecules and disorder among the pyrazine rings reveal additional influences on the positions of the pyrazine band and, therefore, on the absorption spectra of the crystal. The results show a magnification of the peak correlated with the MLCT in the HS state and a significant red shift of the LS characteristic absorption band. The presented approach involving band structure analysis delivers a more complete image of the electronic properties of the [Fe(pz)2Pt(CN)4] crystalline network and can be a landmark for insightful studies of other MOFs.

Anomalous Pressure Response of Temperature-Induced Spin Transition and a Pressure-Induced Spin Transition in Two-Dimensional Hofmann Coordination Polymers

“…According to the Tanabe–Sugano diagram, the ST accompanied by a dramatic change in Fe–N bond length will seriously affect the d-d charge transfer. Therefore, UV–vis absorption spectroscopy is an effective means to monitor the spin state of metal ions. , Variable-pressure absorption spectra of Isoq-Pt and Isoq-Pd single crystals using silicone oil as PTM were collected as shown in Figure . For Isoq-Pt at ambient pressure, the absorption spectrum is dominated by the metal–ligand charge transfer (MLCT) band.…”

“…According to the Tanabe−Sugano diagram, the ST accompanied by a dramatic change in Fe−N bond length will seriously affect the d-d charge transfer. Therefore, UV−vis absorption spectroscopy is an effective means to monitor the spin state of metal ions 58,59.…”