Theoretical and experimental investigation of novel iron(II)-based spin crossover compounds

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• 作者：Inga Respondek ; Lena Bressel ; Peter Saalfrank ; Holger Kä ; mpf ; Andreas Grohmann
• 关键词：Spin crossover (SCO) compounds ; High-spin– ; low-spin splitting energies ; Vibrations and IR spectra ; Excited states and UV/vis absorption spectra ; Switching via light induced excited state spin trapping
• 刊名：Chemical Physics
• 出版年：2008
• 期刊代码：18_03010104
• 类别：ch
• 出版时间：23 May 2008
• 卷：347
• 期：1-3
• 页码：514-522
• 文件大小：678 K

摘要

Two novel spin crossover (SCO) compounds, namely [Fe(INMe)(pyN₄)]Br₂, and [Fe(IMMe)(pyN₄)](OTf)₂, where pyN₄ = 2,6-Bis(1′,3′-diamino-2′methyl-prop-2′yl)pyridine, INMe = isonicotinic acid methyl ester, IMMe = N-methyl-imidazole, and OTf = triflate, are characterized here both from experimental and theoretical viewpoints. In particular, we apply various density functionals and basis sets to obtain optimized geometries for low- (LS) and high-spin (HS) states, vibrational spectra, LS–HS splittings, and temperature-dependent UV/vis spectra. While geometries and spectra are in good agreement with experimental data, the well-known spin pairing problem makes it difficult to compute accurate LS–HS splitting energies and enthalpies. Based on TD–DFT calculations, the capacity of the compounds for use as reversibly photo-switchable molecules is discussed.