Tetrakis(thiadiazole)porphyrazines. 2. Metal complexes with Mn(I), Fe(II),Co(II), Ni(II), and Zn(II)

The synthesis and general chemical physical characterization of the followi ng new classes of complexes derived from tetrakis(thiadiazole)porphyrazine (TTDPzH(2)), i.e., [(TTDPz)M(DMSO)(2)] (M = Mn(II), Fe(III)), [(TTDPz)M]-(H 2O)(2), and [(TTDPz)M] (M = Mn(II), Fe(II), Co(II), Ni(II), Zn(II)) are rep orted. The IR spectra in the region 4000-200 cm(-1) show for all the specie s typical modes of the TTDPz skeleton and specific absorptions of the thiad iazole ring. The UV-visible spectra in different media show the expected ab sorptions in the Soret and Q-band regions. Inspection of the IR spectra of the two six-coordinate adducts [(TTDPz)M(DMSO)(2)] and of their correspondi ng species containing DMSO-d(6) clearly indicate that DMSO is O-bonded to t he central metal in both species (v(SO) located at 918 and 940 cm(-1) for t he Fe(II) and Mn(II) species, respectively), differently from the findings for DMSO (S-bonded) in the Fe(II) and Ru(II) phthalocyanine analogues. The complexes [(TTDPz)M]-(H2O)(2) and [(TTDPz)M] are all tetracoordinate specie s, the water molecules for the hydrated species being very likely only weak ly ligated at the peripheral thiadiazole rings of the macrocycle. Some addi tional information on the oxidation and spin stare of the complexes has bee n achieved by Mossbauer spectra (Fe) and room-temperature magnetic suscepti bility measurements, and data at hand are compared, when allowed, with thos e of the parallel classes of metal phthalocyanine complexes.