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

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

研究成果: Article査読

2 被引用数 (Scopus)

抄録

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.

本文言語English
ページ(範囲)4534-4542
ページ数9
ジャーナルNew Journal of Chemistry
40
5
DOI
出版ステータスPublished - 2016

ASJC Scopus subject areas

  • 触媒
  • 化学 (全般)
  • 材料化学

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