Preparation of dihydroquinazoline carbohydrazone Fe(II) complexes for spin crossover

Fu Xing Shen, Wei Huang, Takashi Yamamoto, Yasuaki Einaga, Dayu Wu

Research output: Contribution to journalArticle

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Abstract

Dihydroquinazoline FeII complexes, namely [Fe(pq-R)2](X)2·xCH3OH·yCH3CN·zH2O (R = 2-py: X = ClO4 -, x = 1, y = 0, z = 2 (1), BF4 -, x = 0, y = 2, z = 1.75 (2), CF3SO3 -, x = 1, y = 1, z = 0 (3); and X = ClO4 -: R = 2-OCH3, x = 0, y = 0, z = 1 (4), R = 3-OCH3, x = 0, y = 0, z = 1 (5)), were prepared and the effects of the solvent, counteranion and ligand substituent on spin crossover properties were discussed. Comparison of X-ray diffraction data for these complexes revealed the sole presence of high-spin FeII at 298 K and the bond distances around the FeII center at low temperature fall much closer to those at high temperature, which is consistent with variable-temperature dc magnetic susceptibility data. However, the loss of solvent induced a significant change in the spin state of complexes 1 and 2. Moreover, fits to magnetic data of the desolvated samples provide crossover temperatures of T1/2 = 182.9(6), 157.0(8) and 138.3(5) K for 1-des (ClO4 -), 2-des (BF4 -) and 3-des (CF3SO3 -), respectively, indicative of the anion-dependent transition temperature. The cooperativity operating in the complexes is thought to be mainly from the intermolecular π⋯π interactions between dihydroquinazoline rings on the neighboring molecules. The ligand substituent effect was also investigated on FeII SCO properties. This work revealed the spin crossover properties of new types of dihydroquinazoline Fe(ii) complexes, including the transition temperature, the degree of completion and the cooperative nature of the transition, which can be optimally designed when developing new spin-crossover materials.

Original languageEnglish
Pages (from-to)4534-4542
Number of pages9
JournalNew Journal of Chemistry
Volume40
Issue number5
DOIs
Publication statusPublished - 2016

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Superconducting transition temperature
Ligands
Temperature
Magnetic susceptibility
Anions
Negative ions
X ray diffraction
Molecules
perchlorate

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Materials Chemistry

Cite this

Preparation of dihydroquinazoline carbohydrazone Fe(II) complexes for spin crossover. / Shen, Fu Xing; Huang, Wei; Yamamoto, Takashi; Einaga, Yasuaki; Wu, Dayu.

In: New Journal of Chemistry, Vol. 40, No. 5, 2016, p. 4534-4542.

Research output: Contribution to journalArticle

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