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

Abstract

The synthesis and general chemical physical characterization of the following new classes of complexes derived from tetrakis(thiadiazole)porphyrazine (TTDPzH(2)), i.e., [(TTDPz)M(DMSO)(2)] (M = Mn(II), Fe(II)), [(TTDPz)M](H(2)O)(2), and [(TTDPz)M] (M = Mn(II), Fe(II), Co(II), Ni(II), Zn(II)) are reported. The IR spectra in the region 4000-200 cm(-)(1) show for all the species typical modes of the TTDPz skeleton and specific absorptions of the thiadiazole ring. The UV-visible spectra in different media show the expected absorptions 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 corresponding species containing DMSO-d(6) clearly indicate that DMSO is O-bonded to the central metal in both species (nu(SO) located at 918 and 940 cm(-)(1) for the 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](H(2)O)(2) and [(TTDPz)M] are all tetracoordinate species, the water molecules for the hydrated species being very likely only weakly ligated at the peripheral thiadiazole rings of the macrocycle. Some additional information on the oxidation and spin state of the complexes has been achieved by Mössbauer spectra (Fe) and room-temperature magnetic susceptibility measurements, and data at hand are compared, when allowed, with those of the parallel classes of metal phthalocyanine complexes.

Molecular Structure of Tetrakis(1,2,5-thiadiazolo)-porphyrazinatozinc(II) in Gaseous Phase

“…[7] The electron diffraction patterns and the mass spectra were recorded simultaneously using a combined GED/MS unit based on EMR-100 and АPDМ-1 devices. [8,9] The sample of [ZnTTDPz] synthesized as described previously [10] was evaporated from a molybdenum effusion cell. The evaporation temperature was measured by a W/Re-5/20 thermocouple.…”

Highly-oriented molecular arrangements and enhanced magnetic interactions in thin films of CoTTDPz using PTCDA templates

“…7,8 The obtained CoTTDPz was purified by vacuum sublimation with a continuous N 2 gas flow (40-50 ml min À1 ). Commercial PTCDA (purity 498%) was used without further purification.…”

“…6 The related metallo-tetrakis(1,2,5-thiadiazole)porphyrazines (MTTDPzs; Fig. 1(b)), which were first synthesized by Ercolani, Stuzhin and their coworkers, 7,8 consist of a central metal ion and a porphyrazine ring annulated with thiadiazole rings. Although the molecular framework of MTTDPzs is similar to that of MPc, their crystal structures and electronic properties are very distinct.…”

Multi-Dimensional Crystal Structures and Unique Solid-State Properties of Heterocyclic Thiazyl Radicals and Related Materials

“…Such low dimensionality would be disadvantageous for 3D electrical conduction and magnetic ordering. Seeking multi-dimensional 41,42 in which intermolecular and interatomic SÁÁÁN contacts are highly likely to be found. In the next section, we describe the crystal structures of the M-TTDPz series and discuss their packing motifs.…”