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Responsive Four-Coordinate Iron(II) Nodes in FePd(CN)4
Ryo Ohtani1, Hiromu Matsunari2, Takafumi Yamamoto3
1Department of Chemistry, Faculty of Science, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.
Abstract:
Metal node design is crucial for obtaining structurally diverse coordination polymers (CPs) and metal-organic frameworks with desirable properties; however, FeII ions are exclusively six-coordinated. Herein, we present a cyanide-bridged three-dimensional (3D) CP, FePd(CN)4 , bearing four-coordinate FeII ions, which is synthesized by thermal treatment of a two-dimensional (2D) six-coordinate FeII CP, Fe(H2 O)2 Pd(CN)4 ⋅4 H2 O, to remove water molecules. Atomic-resolution transmission electron microscopy and powder X-ray and neutron diffraction measurements revealed that the FePd(CN)4 structure is composed of a two-fold interpenetrated PtS topology network, where the FeII center demonstrates an intermediate geometry between tetrahedral and square-planar coordination. This four-coordinate FeII center with the distorted geometry can act as a thermo-responsive flexible node in the PtS network.
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