TY - JOUR
T1 - Magnetic properties of V-substitution effect in an iron mixed valence complex
AU - Shida, Norihiro
AU - Suzawa, Yoshiki
AU - Inaba, Michikazu
AU - Okazawa, Atsushi
AU - Kojima, Norimichi
AU - Enomoto, Masaya
N1 - Funding Information:
This work was conducted at Advanced Characterization Nanotechnology Platform of the University of Tokyo, supported by “Nanotechnology Platform” of the Ministry of Education, Culture, Sports, Science and Technology ( MEXT ), Japan.
Publisher Copyright:
© 2017 Elsevier Ltd
PY - 2017/11/4
Y1 - 2017/11/4
N2 - The iron mixed-valence complex (n-C3H7)4N[FeIIFeIII(dto)3] (dto = C2O2S2) exhibits a novel type of phase transition according electron transfer between FeII and FeIII called charge transfer phase transition (CTPT). The existence of the CTPT highly depends on the 3d metal substitution with Zn, Mn, Cr, or Co for corresponding Fe site in (n-C3H7)4N[FeIIFeIII(dto)3]. Here, we prepared a series of magnetically diluted complexes (n-C3H7)4N[FeIIFeIII1−xVIIIx(dto)3] (x = 0–1), and carried out investigation of magnetic properties. Judging from the magnetic susceptibility measurement, there is no suppression of the CTPT unlike other 3d metal substituted cases. Moreover, 57Fe Mössbauer spectroscopy revealed that about 60% of FeII sites changed their spin states from high spin to low spin in case of substitution rate for x = 1.00. Since the difference of hardness and softness between metallic ions (FeII, FeIII and VIII) and coordination sites of ligand (O or S in dto), this behavior is explained by the linkage isomerization of bridging ligand in formation process of the complex.
AB - The iron mixed-valence complex (n-C3H7)4N[FeIIFeIII(dto)3] (dto = C2O2S2) exhibits a novel type of phase transition according electron transfer between FeII and FeIII called charge transfer phase transition (CTPT). The existence of the CTPT highly depends on the 3d metal substitution with Zn, Mn, Cr, or Co for corresponding Fe site in (n-C3H7)4N[FeIIFeIII(dto)3]. Here, we prepared a series of magnetically diluted complexes (n-C3H7)4N[FeIIFeIII1−xVIIIx(dto)3] (x = 0–1), and carried out investigation of magnetic properties. Judging from the magnetic susceptibility measurement, there is no suppression of the CTPT unlike other 3d metal substituted cases. Moreover, 57Fe Mössbauer spectroscopy revealed that about 60% of FeII sites changed their spin states from high spin to low spin in case of substitution rate for x = 1.00. Since the difference of hardness and softness between metallic ions (FeII, FeIII and VIII) and coordination sites of ligand (O or S in dto), this behavior is explained by the linkage isomerization of bridging ligand in formation process of the complex.
KW - Charge transfer phase transition
KW - Dilution effect on 3d metal ion
KW - Iron mixed valence complex
KW - Linkage isomerization
KW - Magnetic property
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U2 - 10.1016/j.poly.2017.04.006
DO - 10.1016/j.poly.2017.04.006
M3 - Article
AN - SCOPUS:85018330870
SN - 0277-5387
VL - 136
SP - 143
EP - 148
JO - Polyhedron
JF - Polyhedron
ER -