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Magnetochemistry 2015, 1(1), 72-82; doi:10.3390/magnetochemistry1010072

Abrupt Spin Transition and Chiral Hydrogen-Bonded One-Dimensional Structure of Iron(III) Complex [FeIII(Him)2(hapen)]SbF6 (Him = imidazole, H2hapen = N,N′-bis(2-hydroxyacetophenylidene)ethylenediamine)

1
Department of Chemistry, Faculty of Science, Kumamoto University, Kurokami 2-39-1, Chuo-ku, Kumamoto 860-8555, Japan
2
Department of Chemistry, Faculty of Science, Okayama University, Tsuchima-naka, Okayama 700-0082, Japan
*
Author to whom correspondence should be addressed.
Academic Editor: Guillem Aromí
Received: 2 October 2015 / Revised: 6 November 2015 / Accepted: 9 November 2015 / Published: 11 December 2015
(This article belongs to the Special Issue Spin Crossover (SCO) Research)
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Abstract

Solvent-free spin crossover (SCO) iron(III) complex, [FeIII(Him)2(hapen)]SbF6 (Him = imidazole, H2hapen = N,N′-bis(2-hydroxyacetophenylidene)ethylenediamine), is synthesized. The FeIII ion has an octahedral coordination geometry, with N2O2 donor atoms of hapen and N2 atoms of two imidazoles at the axial positions. The saturated five-membered chelate ring of hapen moiety assumes a gauche-type δ- or λ-conformation to give chiral species of δ-[FeIII(Him)2(hapen)]+ or λ-[FeIII(Him)2(hapen)]+. One imidazole is hydrogen-bonded to phenoxo oxygen atom of hapen of the adjacent unit to give a hydrogen-bonded chiral one-dimensional structure, {δ-[FeIII(Him)2(hapen)]+}1∞ or {λ-[FeIII(Him)2(hapen)]+}1∞. The adjacent chains with the opposite chiralities are arrayed alternately. The temperature dependences of the magnetic susceptibilities revealed an abrupt one-step spin transition between high-spin (S = 5/2) and low-spin (S = 1/2) states at the spin transition temperature of T1/2 = 105 K. The crystal structures were determined at 296 and 100 K, where the populations of HS:LS of high- and low-spin ratio are evaluated to be 1:0 and 0.3:0.7, respectively, based on magnetic measurements. During the spin transition from 296 K to 100 K, the average Fe–N distance and O–Fe–O angle decrease to a regular octahedron by 0.16 Å and 13.4°, respectively. The structural change in the coordination environment is transmitted to the adjacent spin crossover (SCO) sites along the chiral 1D chain through hydrogen-bonds. The abrupt SCO profile and the spin transition temperature for the isomorphous compounds [FeIII(Him)2(hapen)]Y (Y = PF6, AsF6, SbF6) are ascribed to the chiral hydrogen-bonded 1D structure and chain-anion interaction. View Full-Text
Keywords: iron(III) complex; imidazole; N2O2 Schiff-base; hydrogen-bond; one-dimensional structure; chiral chain iron(III) complex; imidazole; N2O2 Schiff-base; hydrogen-bond; one-dimensional structure; chiral chain
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Ueno, T.; Miyano, K.; Hamada, D.; Ono, H.; Fujinami, T.; Matsumoto, N.; Sunatsuki, Y. Abrupt Spin Transition and Chiral Hydrogen-Bonded One-Dimensional Structure of Iron(III) Complex [FeIII(Him)2(hapen)]SbF6 (Him = imidazole, H2hapen = N,N′-bis(2-hydroxyacetophenylidene)ethylenediamine). Magnetochemistry 2015, 1, 72-82.

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