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meso-Diaryltetrabenzo(opp)diazaporphyrins are made readily available via Curtius rearrangement of azidocarbonyl derivatives of meso-aryldibenzodipyrromethenes, readily generated with or without isolation from tert-butoxycarbonyl derivatives of the same system. The new tetrapyrrolic dyes are isostructural with 5,15-diaryltetrabenzoporphyrins and resemble both phthalocyanines and tetrabenzoporphyrins to afford an interesting new system for optical applications and material research.

The metal complexes of a pivotal representative of the socalled porphyrin-phthalocyanine hybrid series -5,15-diaryl-10,20-diazatetrabenzoporphyrin (Ar 2 TBDAP), -recently made available by a new selective and versatile procedure, with Zn, Ni, Cu, and Pd were synthesized and characterized by single crystal X-ray analysis, UV-vis/NIR absorption and emission spectroscopy, nanosecond and microsecond time-resolved (NSTA and TCSPC) experiments and by means of cyclic voltammetry. The complexes obtained are compared with the related tetra-benzo-annelated tetrapyrrolic systems, including tetrabenzoporphyrin, phthalocyanine, and other hybrids, using both experimental data and the results of quantum chemical DFT and TD-DFT computations. The Ar 2 TBDAP system reported shares sharp hyperchromic long-wavelength absorption of phthalocyanines with the essential features of extended porphyrins including the possibilities of effective chemical modification through meso-aryl substituents.

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