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Inorganics 2017, 5(3), 53; doi:10.3390/inorganics5030053

Halogen Substituent Effect on the Spin-Transition Temperature in Spin-Crossover Fe(III) Compounds Bearing Salicylaldehyde 2-Pyridyl Hydrazone-Type Ligands and Dicarboxylic Acids

1
Institute for Materials Chemistry and Engineering, Kyushu University, 744 Motoka, Nishi-ku, Fukuoka 819-0395, Japan
2
Department of Basic Science, Graduation School of Arts and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo 153-8902, Japan
*
Author to whom correspondence should be addressed.
Received: 29 June 2017 / Revised: 17 July 2017 / Accepted: 11 August 2017 / Published: 12 August 2017
(This article belongs to the Special Issue Spin-Crossover Complexes)
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Abstract

Four Fe(III) spin-crossover (SCO) compounds, [Fe(HL1)2](HCl4TPA) (1-Cl), [Fe(HL1)2](HBr4TPA) (1-Br), [Fe(HL2)2](HCl4TPA) (2-Cl), and [Fe(HL2)2](HBr4TPA) (2-Br) (HL1 = 4-chloro-2-nitro-6-(1-(2-(pyridine-2-yl)hydrazono)ethyl)phenolate; HL2 = 4-bromo-2-nitro-6-(1-(2-(pyridine-2-yl)hydrazono)ethyl)phenolate; HCl4TPA = 2,3,5,6-tetrachloro-4-carboxybenzoate; and HBr4TPA = 2,3,5,6-tetrabromo-4-carboxybenzoate), were synthesized to investigate the halogen substituent change effect in salicylaldehyde 2-pyridyl hydrazone-type ligands and dicarboxylic acids in SCO complexes to the spin-transition temperature. Crystal structure analyses showed that these compounds were isostructural. In addition, a one-dimensional hydrogen–bonded column was formed by the dicarboxylic acid anion and weak hydrogen bonds between the Fe(III) complexes. From Mössbauer spectroscopy and magnetic property measurements, these compounds were confirmed to exhibit gradual SCO. The spin-transition temperature can be shifted by changing the halogen substituent in the salicylaldehyde 2-pyridyl hydrazone-type ligands and dicarboxylic acids without changing the molecular arrangement in the crystal packing. View Full-Text
Keywords: spin crossover; hydrazone complex; dicarboxylic acid spin crossover; hydrazone complex; dicarboxylic acid
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Nakanishi, T.; Okazawa, A.; Sato, O. Halogen Substituent Effect on the Spin-Transition Temperature in Spin-Crossover Fe(III) Compounds Bearing Salicylaldehyde 2-Pyridyl Hydrazone-Type Ligands and Dicarboxylic Acids. Inorganics 2017, 5, 53.

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