Structures and spin states of bis(tridentate)-type mononuclear and triple helicate dinuclear iron(II) complexes of imidazole-4-carbaldehyde azine.

Abstract

Mononuclear [Fe(H(2)L(R))(2)](2+) and dinuclear [Fe(2)(H(2)L(R))(3)](4+) (R = H, 2-Me, 5-Me) complexes containing the new imidazole-4-carbaldehyde azine ligand (H(2)L(H)) and its derivatives (H(2)L(2-Me) and H(2)L(5-Me)) prepared from the condensation reaction of 4-formylimidazole or 2-methyl- or 5-methyl-4-formylimidazole with hydrazine (2:1) were prepared, and their magnetostructural relationships were studied. In the mononuclear complexes, H(2)L(R) acts as an unsymmetrical tridentate ligand with two imidazole nitrogen atoms and one azine nitrogen atom, while in the dinuclear complexes, H(2)L(R) acts as a dinucleating ligand employing four nitrogen atoms to form a triple helicate. At room temperature, [Fe(2)(H(2)L(H))(3)](ClO(4))(4) and [Fe(2)(H(2)L(2-Me))(3)](ClO(4))(4) were in the high-spin (HS) and low-spin (LS) states, respectively. The results are in accordance with the ligand field strength of H(2)L(2-Me) with electron-donating methyl groups being stronger than H(2)L(H), with the order of the ligand field strengths being H(2)L(2-Me) > H(2)L(H). However, in the mononuclear [Fe(H(2)L(H))(2)](ClO(4))(2) and [Fe(H(2)L(2-Me))(2)](ClO(4))(2) complexes, a different order of ligand field strengths, H(2)L(H) > H(2)L(2-Me), was observed because [Fe(H(2)L(H))(2)](ClO(4))(2) was in the LS state while [Fe(H(2)L(2-Me))(2)](ClO(4))(2) was in the HS state at room temperature. X-ray structural studies revealed that the interligand steric repulsion between a methyl group of an H(2)L(2-Me) ligand and the other ligand in [Fe(H(2)L(2-Me))(2)](ClO(4))(2) is responsible for the observed change in the spin state. Two kinds of crystals, needles and blocks, were isolated for [Fe(2)(H(2)L(H))(3)](BF(4))(4), and both exhibited a sharp spin transition, [LS-HS] <--> [HS-HS]. The spin transition of the block crystals is more abrupt with a hysteresis, T(c) upward arrow = 190 K and T(c) downward arrow = 183 K with DeltaT = 7 K.

DOI: 10.1021/ic900977m

Cite this paper

@article{Sunatsuki2009StructuresAS, title={Structures and spin states of bis(tridentate)-type mononuclear and triple helicate dinuclear iron(II) complexes of imidazole-4-carbaldehyde azine.}, author={Yukinari Sunatsuki and Ryohei Kawamoto and Kunihiro Fujita and Hisashi Maruyama and Takayoshi Suzuki and Hiroyuki Ishida and Masaaki Kojima and Seiichiro Iijima and Naohide Matsumoto}, journal={Inorganic chemistry}, year={2009}, volume={48 18}, pages={8784-95} }