Oxidation of 2-amino-substituted BODIPYs afforded BODIPY trimers in a one-step operation. The trimer consists of a pyrazine-fused BODIPY dimer to which one BODIPY unit is connected through an NH linkage. Effective expansion of π-conjugation over the fused dimer was observed in optical and electrochemical measurements.
Preparation of 5,15-dithiaporphyrin copper(II) complex was carried out by treatment of 5,15-dithiaporphyrin free-base with copper(II) acetate. X-ray diffraction analysis elucidated its dimeric structure in the solid state, in which the meso-sulfur atom served as an axial ligand to each pentacoordinated Cu ( II ) center. Temperature dependent magnetic susceptibility of the complex was measured to reveal the weak antiferromagnetic interaction between two Cu ( II ) centers in the solid state. 5,15-dithiaporphyrin Cu ( II ) complex was converted into 10-thiacorrole Cu ( II ) complex in good yield upon heating with triphenylphosphine in refluxing toluene.
Oxidation of 5,15-dithiaporphyrin with meta-chloroperbenzoic acid afforded the corresponding S,S-tetraoxide in good yield.T he resultant5 ,5,15,15-tetraoxo-5,15-dithiaporphyrin exhibited the highly electron-deficient nature as elucidated by the electrochemical analysis and theoretical calculations. Treatment of tetraoxodithiaporphyrin with zinc(II) acetate and nickel(II) acetate provided the corresponding metal complexes efficiently.O wing to its enhanced Lewis acidity of the metal center by the electron-deficient ligand, the nickel complex underwentf acile axial ligationt o form pentacoordinatea nd hexacoordinate high-spin( S = 1) complexes in solution and solid, respectively.T he binding constant of pyridine to the Ni II centerw as significantly highert han those of conventionalp orphyrin Ni II complexes. Te mperature-dependent magnetic susceptibility measurementso ft he high-spin Ni II complex revealed the presence of weak ferromagnetic interactions.
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