Abstract
Assembled complexes, [Fe(NCX)2(bpanth)2]n (X = S, Se, BH3; bpanth = 9,10-bis(4-pyridyl)anthracene), were synthesized. The iron for the three complexes was in temperature-independent high spin state by 57Fe Mössbauer spectroscopy and magnetic susceptibility measurement. X-ray structural analysis revealed the interpenetrated structure of [Fe(NCS)2(bpanth)2]n. In the local structure around the iron atom, the coordinated pyridine planes were shown to be a parallel type, which is in accordance with the results investigated by density functional theory (DFT) calculation. This complex (X = S) has CH–π interactions between the H atom of coordinated pyridine and the neighboring anthracene of the other 2D grid. It was suggested that the interpenetrated structure was supported by the stabilization of CH–π interaction, and this intermolecular interaction forced the relatively unstable parallel structure. That is, the unstable local structure is compensated by the stabilization due to intermolecular interaction, which controlled the spin state as high spin state.
Highlights
Iron(II) octahedral assembled complexes can take two spin states (high spin (HS); S = 2 and low spin (LS); S = 0) in intermediate ligand field [1]
Assembled complexes have an important position in the spin-crossover chemistry [2,3], because they have a variety of structures and the spin state is sometimes controlled by the adsorption/desorption of guest molecules
The obtained single crystal of complex 1 was analyzed by XRD, and the structure was Figure 5 illustrates the local structure around the iron atom
Summary
Iron(II) octahedral assembled complexes can take two spin states (high spin (HS); S = 2 and low spin (LS); S = 0) in intermediate ligand field [1]. Assembled complexes have an important position in the spin-crossover chemistry [2,3], because they have a variety of structures and the spin state is sometimes controlled by the adsorption/desorption of guest molecules. The change of complex structure and the intermolecular interaction were predicted to influence the SCO phenomenon. The SCO behavior of iron(II) assembled complexes is related to the dihedral angle of pyridine ligands to Fe–NCX. There is a possibility that the weak π-accepter property of pyridine affects the spin state depending on the local structure around iron atom
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