Perhalogenated porphyrinic derivatives with indium and thallium: The X-ray structures of (β-Cl₄TPP)Tl(Cl), (β-Cl₄TPP)In(Cl) and (TpFTPP)Tl(Cl)

The synthesis and spectroscopic characterization of new substituted porphyrinate complexes are reported. The investigated compounds are represented by the formula (Porph)M(Cl) where Porph are TpFPP, TPyP, β-Cl ₄TPP, β-Cl₈TPP or β-Cl₄TPP, and M=In or Tl. UV-Vis and NMR spectroscopies of the title complexes confirm the proposed molecular formula and are described extracting all plausible information. The study is completed by three X-ray structures of (β-Cl₄TPP)Tl(Cl) , (β-Cl₄TPP)In(Cl) and (TpFTPP)Tl(Cl). Compounds (β-Cl ₄TPP)Tl(Cl) and (β-Cl₄TPP)In(Cl) are isostructural and they were treated in a similar way. The chloride substituents on the porphyrin core were found to be disordered in both compounds and they were refined anisotropically with occupation factors free to vary. The porphyrin core is saddle distorted while there is no twist distortion as judged by the large values of the dihedral angles formed between the phenyl rings and the C ₂₀N₄ mean plane. In compound (TpFTPP)In(Cl), the dihedral angles between the pentafluorophenyl rings and C₂₀N₄ are very close to the ideal value of 90°.