Syntheses, hydrogen-bonded assembly structures, and spin crossover properties of [FeIII(Him)2(n-MeOhapen)]PF6 (Him = imidazole and n-MeOhapen = N,N′-bis(n-methoxy-2-oxyacetophenylidene)ethylenediamine); n = 4, 5, 6)

Takeshi Fujinami; Mizuki Ikeda; Masataka Koike; Naohide Matsumoto; Tomohiro Oishi; Yukinari Sunatsuki

doi:10.1016/j.ica.2015.03.034

Syntheses, hydrogen-bonded assembly structures, and spin crossover properties of [Fe^III(Him)₂(n-MeOhapen)]PF₆ (Him = imidazole and n-MeOhapen = N,N′-bis(n-methoxy-2-oxyacetophenylidene)ethylenediamine); n = 4, 5, 6)

Takeshi Fujinami, Mizuki Ikeda, Masataka Koike, Naohide Matsumoto, Tomohiro Oishi, Yukinari Sunatsuki

Advanced Science Research Center

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

Abstract

Three iron(III) complexes, [Fe^III(Him)₂(n-MeOhapen)]PF₆ (1: n = 4, 2: n = 5, 3: n = 6), where Him = imidazole and n-MeOhapen = N,N′-bis(n-methoxy-2-oxyacetophenylidene)ethylenediamine, were synthesized. Each Fe^III ion was coordinated by N₄O₂ donor atoms of equatorial n-MeOhapen and two axial Him. The saturated FeC₂N₂ chelate ring involving the ethylenediamine moiety adopted a gauche conformation and the two phenylidene planes of [Fe^III(Him)₂(n-MeOhapen)]⁺ were oriented opposite to the FeO₂N₂ coordination plane. Two adjacent [Fe^III(Him)₂(4-MeOhapen)]⁺ cations in 1 were connected via PF₆^- ions by hydrogen bonds between the imidazole group and PF₆^- to give a one-dimensional chain. Two adjacent cations in 2 were connected via hydrogen bonds between the phenylidene oxygen and imidazole atoms to form a cyclic dimer structure. Two EtOH molecules were involved in a hydrogen-bonded cyclic dimer structure in 3. Compounds 1 and 2 showed spin crossover behavior, but 3 showed incomplete spin crossover.

Original language	English
Pages (from-to)	89-95
Number of pages	7
Journal	Inorganica Chimica Acta
Volume	432
DOIs	https://doi.org/10.1016/j.ica.2015.03.034
Publication status	Published - Jun 1 2015

Keywords

Assembly structures
Hydrogen bonds
Imidazole
Iron(III) complex
NO Schiff-base ligand
Spin equilibrium

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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Fujinami, T., Ikeda, M., Koike, M., Matsumoto, N., Oishi, T., & Sunatsuki, Y. (2015). Syntheses, hydrogen-bonded assembly structures, and spin crossover properties of [Fe^III(Him)₂(n-MeOhapen)]PF₆ (Him = imidazole and n-MeOhapen = N,N′-bis(n-methoxy-2-oxyacetophenylidene)ethylenediamine); n = 4, 5, 6). Inorganica Chimica Acta, 432, 89-95. https://doi.org/10.1016/j.ica.2015.03.034

Syntheses, hydrogen-bonded assembly structures, and spin crossover properties of [Fe^III(Him)₂(n-MeOhapen)]PF₆ (Him = imidazole and n-MeOhapen = N,N′-bis(n-methoxy-2-oxyacetophenylidene)ethylenediamine); n = 4, 5, 6). / Fujinami, Takeshi; Ikeda, Mizuki; Koike, Masataka et al.

In: Inorganica Chimica Acta, Vol. 432, 01.06.2015, p. 89-95.

Research output: Contribution to journal › Article › peer-review

Fujinami, T, Ikeda, M, Koike, M, Matsumoto, N, Oishi, T & Sunatsuki, Y 2015, 'Syntheses, hydrogen-bonded assembly structures, and spin crossover properties of [Fe^III(Him)₂(n-MeOhapen)]PF₆ (Him = imidazole and n-MeOhapen = N,N′-bis(n-methoxy-2-oxyacetophenylidene)ethylenediamine); n = 4, 5, 6)', Inorganica Chimica Acta, vol. 432, pp. 89-95. https://doi.org/10.1016/j.ica.2015.03.034

Fujinami T, Ikeda M, Koike M, Matsumoto N, Oishi T, Sunatsuki Y. Syntheses, hydrogen-bonded assembly structures, and spin crossover properties of [Fe^III(Him)₂(n-MeOhapen)]PF₆ (Him = imidazole and n-MeOhapen = N,N′-bis(n-methoxy-2-oxyacetophenylidene)ethylenediamine); n = 4, 5, 6). Inorganica Chimica Acta. 2015 Jun 1;432:89-95. https://doi.org/10.1016/j.ica.2015.03.034

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title = "Syntheses, hydrogen-bonded assembly structures, and spin crossover properties of [FeIII(Him)2(n-MeOhapen)]PF6 (Him = imidazole and n-MeOhapen = N,N′-bis(n-methoxy-2-oxyacetophenylidene)ethylenediamine); n = 4, 5, 6)",

abstract = "Three iron(III) complexes, [FeIII(Him)2(n-MeOhapen)]PF6 (1: n = 4, 2: n = 5, 3: n = 6), where Him = imidazole and n-MeOhapen = N,N′-bis(n-methoxy-2-oxyacetophenylidene)ethylenediamine, were synthesized. Each FeIII ion was coordinated by N4O2 donor atoms of equatorial n-MeOhapen and two axial Him. The saturated FeC2N2 chelate ring involving the ethylenediamine moiety adopted a gauche conformation and the two phenylidene planes of [FeIII(Him)2(n-MeOhapen)]+ were oriented opposite to the FeO2N2 coordination plane. Two adjacent [FeIII(Him)2(4-MeOhapen)]+ cations in 1 were connected via PF6- ions by hydrogen bonds between the imidazole group and PF6- to give a one-dimensional chain. Two adjacent cations in 2 were connected via hydrogen bonds between the phenylidene oxygen and imidazole atoms to form a cyclic dimer structure. Two EtOH molecules were involved in a hydrogen-bonded cyclic dimer structure in 3. Compounds 1 and 2 showed spin crossover behavior, but 3 showed incomplete spin crossover.",

keywords = "Assembly structures, Hydrogen bonds, Imidazole, Iron(III) complex, NO Schiff-base ligand, Spin equilibrium",

author = "Takeshi Fujinami and Mizuki Ikeda and Masataka Koike and Naohide Matsumoto and Tomohiro Oishi and Yukinari Sunatsuki",

note = "Funding Information: T. Fujinami was supported by the Research Fellowship for Young Scientists of the Japan Society for the Promotion of Science , KAKENHI 00248556 . Publisher Copyright: {\textcopyright} 2015 Elsevier B.V. All rights reserved.",

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doi = "10.1016/j.ica.2015.03.034",

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T1 - Syntheses, hydrogen-bonded assembly structures, and spin crossover properties of [FeIII(Him)2(n-MeOhapen)]PF6 (Him = imidazole and n-MeOhapen = N,N′-bis(n-methoxy-2-oxyacetophenylidene)ethylenediamine); n = 4, 5, 6)

AU - Fujinami, Takeshi

AU - Ikeda, Mizuki

AU - Koike, Masataka

AU - Matsumoto, Naohide

AU - Oishi, Tomohiro

AU - Sunatsuki, Yukinari

N1 - Funding Information: T. Fujinami was supported by the Research Fellowship for Young Scientists of the Japan Society for the Promotion of Science , KAKENHI 00248556 . Publisher Copyright: © 2015 Elsevier B.V. All rights reserved.

PY - 2015/6/1

Y1 - 2015/6/1

N2 - Three iron(III) complexes, [FeIII(Him)2(n-MeOhapen)]PF6 (1: n = 4, 2: n = 5, 3: n = 6), where Him = imidazole and n-MeOhapen = N,N′-bis(n-methoxy-2-oxyacetophenylidene)ethylenediamine, were synthesized. Each FeIII ion was coordinated by N4O2 donor atoms of equatorial n-MeOhapen and two axial Him. The saturated FeC2N2 chelate ring involving the ethylenediamine moiety adopted a gauche conformation and the two phenylidene planes of [FeIII(Him)2(n-MeOhapen)]+ were oriented opposite to the FeO2N2 coordination plane. Two adjacent [FeIII(Him)2(4-MeOhapen)]+ cations in 1 were connected via PF6- ions by hydrogen bonds between the imidazole group and PF6- to give a one-dimensional chain. Two adjacent cations in 2 were connected via hydrogen bonds between the phenylidene oxygen and imidazole atoms to form a cyclic dimer structure. Two EtOH molecules were involved in a hydrogen-bonded cyclic dimer structure in 3. Compounds 1 and 2 showed spin crossover behavior, but 3 showed incomplete spin crossover.

AB - Three iron(III) complexes, [FeIII(Him)2(n-MeOhapen)]PF6 (1: n = 4, 2: n = 5, 3: n = 6), where Him = imidazole and n-MeOhapen = N,N′-bis(n-methoxy-2-oxyacetophenylidene)ethylenediamine, were synthesized. Each FeIII ion was coordinated by N4O2 donor atoms of equatorial n-MeOhapen and two axial Him. The saturated FeC2N2 chelate ring involving the ethylenediamine moiety adopted a gauche conformation and the two phenylidene planes of [FeIII(Him)2(n-MeOhapen)]+ were oriented opposite to the FeO2N2 coordination plane. Two adjacent [FeIII(Him)2(4-MeOhapen)]+ cations in 1 were connected via PF6- ions by hydrogen bonds between the imidazole group and PF6- to give a one-dimensional chain. Two adjacent cations in 2 were connected via hydrogen bonds between the phenylidene oxygen and imidazole atoms to form a cyclic dimer structure. Two EtOH molecules were involved in a hydrogen-bonded cyclic dimer structure in 3. Compounds 1 and 2 showed spin crossover behavior, but 3 showed incomplete spin crossover.

KW - Assembly structures

KW - Hydrogen bonds

KW - Imidazole

KW - Iron(III) complex

KW - NO Schiff-base ligand

KW - Spin equilibrium

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