Synthesis of Hofmann-type Zn(H$_2$O)$_2$Ni(CN)$_4$.nG (G = water and 1,4-dioxane) clathrates and the determination of their structural properties by various spectroscopic methods

Authors: ZEKİ KARTAL, ONUR ŞAHİN, ABDÜLKERİM YAVUZ

Abstract: Two new 2-dimensional cyanide-bridged coordination polymers [Zn(H$_{2}$O)$_{2}$Ni(CN)$_{4}$ 6(H$_{2}$O) and Zn(H$_{2}$O)$_{2}$ Ni(CN)$_{4}$ 3(C$_{4}$H$_{8}$O$_{2})$], which were similar to Hofmann-type clathrates, were synthesized based on [Ni(CN)$_{4}$]$^{2-}$ and Zn$^{2+}$ as building blocks. These substances were synthesized as compounds in crystalline form. Thes tructures of the crystalline compounds were characterized via their spectral analyses. General information about the structures of the newly obtained Hofmann-type clathrates was obtained from their vibration spectra by considering significant changes in the vibration peaks of the cyanide group, water ligand molecule, and guest molecules (water and 1,4-dioxane). The thermal behavior of the Hofmann-type clathrates was investigated in the range of 25-500 $^{\circ}$ C. In addition, experimental data on the magnetic properties of the Hofmann-type clathrates were obtained using the Gouy method under normal conditions. Information on the properties of the structures of the Hofmann clathrates was obtained by applying the single crystal diffraction technique. The asymmetric unit of the first Hofmann-type clathrate contained 1 Zn(II) ion, 1 Ni(II) ion, 1 cyanide ligand, 1 water ligand molecule, and 2 guest water molecules. The asymmetric unit of the second Hofmann-type clathrate contained 1 Zn(II) ion, 1 Ni(II) ion, 2 cyanide ligands, 1 water ligand molecule, and 2 half guest 1,4-dioxane molecules.

Keywords: Hofmann-type clathrates, vibrational spectra, single crystal X-ray diffraction analysis, host structure, guest molecules

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