Computational Study on Thermal Spin-Crossover Behavior for Coordination Polymers Possessing trans-[Fe(NCS)₂(pyridine)₄] Unit

• Masashi Kaneko

• Satoru Nakashima

抄録

Fe(II) spin-crossover (SCO) phenomenon for fifteen sets of coordination polymers possessing a trans-[Fe(NCS)2(pyridine)4] unit is investigated by means of density functional calculations. Constrained geometry optimization is applied to Fe(NCS)2(pyridine)4 models by fixing the dihedral angle between Fe-NCS axis and pyridine plane. Zero-point corrected energy difference between HS and LS, ΔE0HL, by TPSSh single point calculation reproduces successfully the experimental SCO-on and SCO-off behaviors for most compounds. In order to investigate the origin of whether SCO behavior occurs or not, we perform Mulliken’s overlap population analysis to wavefunction in valence region. Overlap population between d-orbital of Fe atom and all atomic orbitals of six N atoms enables us to assign the kind of d-orbital type molecular orbitals. Calculating ligand field splitting (Δo) obtained by population analysis, we find good correlation between Δo of LS and ΔE0HL indicating that the bonding of LS state depends on the switching behavior of SCO-on/off. Furthermore, combining the ligand field theory with quantum chemical calculation, we obtain the Δo value of the crossing point where ΔE0HL is zero as ca. 4.61 eV.

収録刊行物

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 88 (8), 1164-1170, 2015-08

  Tokyo : Chemical Society of Japan

キーワード

• General Chemistry

詳細情報

• CRID: 1523388079546096256
• NII論文ID: 130005092059
• NII書誌ID: AA00580132
• ISSN: 00092673
• ISSN: 13480634
• DOI: 10.1246/bcsj.20150026
• NDL書誌ID: 026648354
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I026648354
• Web Site: https://academic.oup.com/bcsj/article-pdf/88/8/1164/56278231/bcsj.20150026.pdf
• 本文言語コード: en
• NDL 雑誌分類:
  • ZP1(科学技術--化学・化学工業)
• データソース種別:
  • NDL
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