FT-IR spectroscopic and thermal study of M(1,6-hexanedithiol)Ni(CN)4⋅2(1,4-dioxane) clathrate (M = Mn, Co, Ni and Cd)

In this study, clathrate of 1,6-hexanedithiol-tetracyanonickel-dioxane, given by the formula M(1,6-hexanedithiol)Ni(CN)4⋅2(l,4-dioxane) (M = Mn, Co, Ni and Cd), is obtained for the first time through chemical methods. The FT-IR spectroscopic data in the region of (4000–400) cm−1 was recorded and the IR frequencies were given and explained in detail. The thermal behavior of these clathrates was also investigated by thermo-gravimetric analysis (TGA), differential thermal analysis (DTA) and derivative thermal gravimetric analysis (DTG). The spectral and thermal analyzes results of the newly synthesized clathrate of 1,6-hexanedithiol-tetracyanonickel-dioxane suggest that these clathrates are new examples of the Hofmann-type dioxane clathrates. In our study, the Hofmann-type dioxane clathrates formed by bounding electrons of sulfur-donor atoms of the thiol groups of 1,6-hexanedithiol ligand molecule to transition metal atoms consist of the corrugated |M–Ni(CN)4|∞ polymeric layers which are held in parallel through the chain of (–M–HDT–M–HDT–M–).