Perhalogenated porphyrinic derivatives with indium and thallium: the X-ray structures of (β-Cl 4TPP)Tl(Cl), (β-Cl 4TPP)In(Cl) and (T pFTPP)Tl(Cl)

• Published in: Polyhedron 2004-06, Vol.23 (10), p.1777-1784
• Main Authors: Raptopoulou, Catherina, Daphnomili, Dimitra, Karamalides, Athanassios, Di Vaira, Massimo, Terzis, Aris, Coutsolelos, Athanassios G.
• Format: Article
• Language: English
• Subjects: Indium; Metalloporphyrins; Thallium
• ISSN: 0277-5387
• DOI: 10.1016/j.poly.2004.04.010

The family of indium and thallium porphyrinic derivatives is completed by new complexes represented by the formula (Porph)M(III)Cl. A variety of porphyrin rings such as T pFPP, TPyP, β-Cl 4TPP, β-Cl 8TPP or β-Cl 4TPP were used in order to study their physicochemical behaviour with respect to their ring basicity, by various spectroscopic methods. 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 T pFPP, TPyP, β-Cl 4TPP, β-Cl 8TPP or β-Cl 4TPP, 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-Cl 4TPP)Tl(Cl), (β-Cl 4TPP)In(Cl) and (T pFTPP)Tl(Cl). Compounds (β-Cl 4TPP)Tl(Cl) and (β-Cl 4TPP)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 20N 4 mean plane. In compound (T pFTPP)In(Cl), the dihedral angles between the pentafluorophenyl rings and C 20N 4 are very close to the ideal value of 90°.