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2003, Vol.76, No.6

1207-1213

Study of Intermolecular Interaction for the Spin-Crossover Iron(II) Compounds

Hayami Shinya 1 , Kawajiri Ryo 1 , Juhász Gergely 1 , Kawahara Takayoshi 1 , Hashiguchi Koichiro 1 , Sato Osamu 2 , Inoue Katsuya 3 , Maeda Yonezo 1
1 Department of Chemistry, Faculty of Sciences, Kyushu University6-10-1, Hakozaki, Higashi-ku, Fukuoka 812-8581
2 Kanagawa Academy of Science and TechnologyEast 412, 3-2-1 Sakado, Takatsu-ku, Kawasaki 213-0012
3 Institute for Molecular ScienceMyodaiji, Okazaki 444-8585
https://doi.org/10.1246/bcsj.76.1207

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Abstract

The thermal spin transitions of iron(II) spin-crossover compounds [Fe(PM-iPA)2(NCS)2] (1) and [Fe(PM-iPA)2(NCSe)2] (2) (PM-iPA = N-(2′-pyridylmethyl)-isopropylamine) have occurred at T1/2 = 267 K and 376 K without thermal hysteresis. No light-induced excited spin state trapping (LIESST) effect was observed for compounds 1 and 2 even at 5 K. The iron(II) spin-crossover compounds [Fe(PM-L)2(NCX)2] (PM-A = N-(2′-pyridylmethyl)-aniline, PM-BiA = N-(2′-pyridylmethyl)-4-aminobiphenyl, PM-TeA = N-(2′-pyridylmethyl)-4-aminoterphenyl, PM-PEA = N-(2′-pyridylmethyl)-4-(phenylethynyl)aniline, and PM-AzA = N-(2′-pyridylmethyl)-4-(phenylazo)aniline; X = S and Se) with ligands having π-systems have exhibited the LIESST effect, and the critical LIESST temperature, Tc(LIESST), has been observed. The compounds 1 and 2 are crystallized at Pnna and C2/c at 298 K, respectively, and the space groups of the compounds remained unchanged until 100 K, although the compounds show the spin transition. The molecular packing structure and thermodynamic parameters of the spin transitions calculated from the magnetic susceptibility curves suggest that compounds 1 and 2 have no strong intermolecular interactions between the complexes, while the compounds with π-system ligands form π–π intra- and intermolecular interactions between the ligands. Our conclusion is that the intermolecular interactions play an important role in trapping a light-induced metastatble state.

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