材料科学
笼状水合物
金属有机骨架
谱线
自旋(空气动力学)
金属
结晶学
物理化学
水合物
有机化学
天文
吸附
航空航天工程
化学
冶金
工程类
物理
作者
Adrian Olejnik,Wioletta Kopeć,Dominik Maskowicz,M. Sawczak
标识
DOI:10.1021/acsami.2c22626
摘要
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.
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