Determination of vibrational bands with quantum chemical calculations and vibrational spectroscopic investigation of hofmann type complexes and clathrates of 1-phenylpiperazine

In this study, at first, the vibrational assignments and frequencies of 1-Phenylpiperazine (pp) ligand molecule have been determined both experimentally and theoretically with some quantum chemical calculations. Later Hofmann type complexes and clathrates, formulated as M(pp)2Ni(CN)4 (M = Ni, Co, Cd, Pd or Mn) and M(pp)2Ni(CN)4.2G (M = Ni, Co or Cd and G = Aniline or 1,4-dioxane) have been synthesized chemically for the first time using pp molecule as ligand and their infrared spectra have been reported in the spectroscopic region of the (4000 ? 400) cm-1. The Raman spectra of compounds which possess M = Cd have been also reported in the region of the (2800 ? 1550) cm-1. According to results of these spectra, the structures of compounds have been tried to clarify with the vibrational spectroscopy. In order to support structure analysis, the M, C, H, N elemental, thermo-gravimetric (TGA) and differential thermal (DTA) analysis of all compounds have been made and the compounds which possess M = Ni have been also examined via transmission electron microscope (TEM). All results have suggested that these synthesized M(pp)2Ni(CN)4 (M = Ni, Co, Cd, Pd or Mn) and M(pp)2Ni(CN)4.2G (M = Ni, Co or Cd and G = Aniline or 1,4-dioxane) compounds are similar in structure to the Hofmann-type complexes and clathrates which are represented with M(L)Ni(CN)4 and M(L)Ni(CN)4.nG general formulas, respectively.