X-ray absorption and emission spectroscopies of X-bridged diiron phthalocyanine complexes (FePc)2X (X = C, N, O) combined with DFT study of (FePc)2X and their high-valent diiron oxo complexes.

μ-Nitrido diiron phthalocyanine [PcFe(+3.5)NFe(+3.5)Pc](0) is an efficient catalyst, able to catalyze the oxidation of methane under near-ambient conditions.

Catalytic defluorination of perfluorinated aromatics under oxidative conditions using N-bridged diiron phthalocyanine.

Carbon-fluorine bonds are the strongest single bonds in organic chemistry, making activation and cleavage usually associated with organometallic and reductive approaches particularly difficult. We describe here an efficient defluorination of poly- and perfluorinated aromatics under oxidative conditions catalyzed by the μ-nitrido diiron phthalocyanine complex [(Pc)Fe(III)(μ-N)Fe(IV)(Pc)] under mild conditions (hydrogen peroxide as the oxidant, near-ambient temperatures). The reaction proceeds via the formation of a high-valent diiron phthalocyanine radical cation complex with fluoride axial ligands, [(Pc)(F)Fe(IV)(μ-N)Fe(IV)(F)(Pc(+•))], which was isolated and characterized by UV-vis, EPR, (19)F NMR, Fe K-edge EXAFS, XANES, and Kβ X-ray emission spectroscopy, ESI-MS, and electrochemical techniques.

Synthesis, X-ray crystal structure, UV/visible linear and nonlinear (optical limiting) spectral properties of symmetrical and unsymmetrical porphyrazines with annulated 1,2,5-thiadiazole and 1,4-diamyloxybenzene moieties.

Co-cyclization of 1,2,5-thiadiazole-3,4-dicarbonitrile and 3,6-diamyloxyphthalodinitrile in the presence of magnesium or lithium amylate in amyl alcohol leads to mixtures containing the Mg derivatives of the symmetrical species tetrakis(1,2,5-thiadiazolo)porphyrazine, (S(4))PzH(2), and tetrakis(1,4-diamyloxybenzo)porphyrazine, (A(4))PzH(2), and the low-symmetry macrocycles bearing peripheral 1,2,5-thiadiazole and 1,4-diamyloxybenzene rings in the ratio 1:3, 2:2 (cis and trans), and 3:1, that is, (SA(3))PzH(2), (S(2)A(2))PzH(2), (SASA)PzH(2), and (S(3)A)PzH(2), respectively. The basic Mg materials were converted to the corresponding free-base macrocycles by treatment with CF(3)COOH. The species were separated from the mixtures by chromatography, either as Mg complexes or demetalated materials.