Synthesis, general physicochemical behaviour and magnetic studies of the macrocyclic bis-pyridine derivatives [TTDPzM(py)2]·2H2O (M = MnII, CoII, NiII)

In our extensive work on phthalocyanine-like macrocycles carrying peripherally attached strongly electron-withdrawing 1,2,5-thia/selenodiazol rings we recently reported on the FeII species of formula [TTDPzFe(py)2].2H2O (TTDPz =tetrakis(thiadiazole)porphyrazinato dianion). The present work deals with the synthesis and extended physicochemical studies of the series of related macrocycles [TTDPzM(py)2].2H2O (M =MnII, CoII, NiII). The diffractograms of three solid samples of the NiII complex [TTDPzNi(py)2]⋅2H2O, obtained from different synthetic procedures, indicate that the species is reproducibly obtained. All three samples are isomorphous with each other as shown by their X-ray powder diffractograms. Based on the comparison of the IR spectra of [TTDPzNi(py)2].2H2O and the related desolvated [TTDPzNi], the IR absorption peaks belonging to the pyridine molecules could be identified. The systematic presence of the two water molecules in all three species suggests that forms of contact do exist in the form of hydrogen bonds between them and the S and N atoms present peripherally in the thiadiazole groups of the macrocyclic units. As regard to the elimination of water, the thermograms (in inert atmosphere in the range 25–600 ◦C) indicate in all cases that loss of water occurs below 100 °C but loss of pyridine occurs over a broad range 100–300 °C for the MnII and CoII species whereas for the NiII complex it takes place in the narrow range 200–220 °C. In relation to the parallel series of metallophthalocyanines, i.e. [PcM] (M =MnII, FeII, CoII), it is noted that the NiII analog has not been reported in the literature and in a direct experiment it has been proved that [PcNi] heated in pyridine is obtained unchanged, the different behavior for the NiII TTDPz derivative due to the electron withdrawing effect of the external thiadiazole substituents, which makes favorable axial pyridine coordination in the complex. Completely insoluble in water, the triad of TTDPz derivatives is extremely low-soluble in non-donor or low donor solvents. This precluded any attempt to isolate single crystals for single-crystal X-ray work. Their UV–visible spectra show essential similarities in whatever organic solvent is used with clearly positioned Soret (300–400 nm) and Q-band absorptions (630–650 nm). Variable temperature magnetic susceptibility and magnetization studies reveal that the [TTDPzM (py)2].2H2O complexes all show paramagnetism with ground state spins of 3/2 (MnII), ½ (CoII) and 1 (NiII), supported by fitting the data to spin Hamiltonian formalism, vide infra. Comparisons are made with the magnetism of [PcM] analogues with key differences noted for M =NiII.