Synthesis, Structure, and Redox and Optical Properties of 5,10,15,20-Tetraaryl-5-azaporphyrinium Salts.

The fundamental properties of azaporphyrins can be modulated over a wide range by changing the number of meso-nitrogen atoms. Reported herein are the first examples of 5,10,15,20-tetraaryl-5-azaporphyrinium (MTAMAP) salts, which were prepared via metal-templated cyclization of the corresponding zinc(II) and copper(II) complexes of 10-aryl-1-chloro-19-benzoyl-5,15-dimesityl-10-azabiladiene-ac. The inclusion of one meso-nitrogen atom in the 5,10,15,20-tetraarylporphyrin skeleton considerably changes the redox and optical properties as well as the degree of aromaticity of the porphyrin ring. The present findings suggest that MTAMAP salts would be promising scaffolds for the development of new azaporphyrin-based ionic fluorophores and photosensitizers.

Synthesis and Optical Properties of 1,2,5,10-Tetraphenylanthra[2,3-b]phosphole Derivatives.

1,2,5,10-Tetraphenylanthra[2,3-b]phosphole oxides and 1-methyl-1,2,5,10-tetraphenylanthra[2,3-b]phospholium salts were prepared, and their optical properties were investigated. The substituent at the para position and the fused anthracene moiety were found to exert significant impacts on the fluorescence properties of the P-bridged 2-styrylanthracene skeleton.

Synthesis, Electrochemical Behavior, and Catalytic Activity of Cobalt Complexes of 5,10,15,20-Tetraaryl-5,15-diazaporphyrinoids.

A one-pot synthesis of cobalt(II) complexes of 5,10,15,20-tetraaryl-5,15-diazaporphyrins (CoTADAPs) from the corresponding 5-aryl-1-arylamino-9-chlorodipyrrins and cobalt(II) acetate is reported. The CoTADAPs exhibited characteristic electrochemical behavior and catalyzed the intramolecular cyclization of N-benzyl-N-Boc-3-diazopropan-1-amines, probably via σ-CoIII-alkyl radical intermediates.