[reaction: see text] N-Confused porphyrin (NCP) bearing pentafluorophenyl groups at meso-positions, which were obtained from N-confused dipyrromethane in ca. 20% yield, can form Cu(II) complex as well as Ag(III), Ni(II), and Pd(II) complexes. The square-planar structures of all these metal complexes were elucidated by X-ray single-crystal analyses.

A heavy atom, bromine, was directly substituted into the porphycene macrocycle to promote intersystem crossing by way of spin-orbit coupling. The singlet oxygen production ability of the porphycene is dramatically enhanced, and the highest value of 0.95 for the quantum yield of singlet oxygen generation (PhiDelta) was obtained for the dibrominated porphycene by visible light excitation.

[structure: see text] A pyrrolic macrocycle, beta-tetrakis(trifluoromethyl)porphycene, is the first example of a fluorine-containing porphycene. Four electron-withdrawing CF(3) substituents provide a highly distorted structure and an attractive electron-deficient nature for the porphycene framework. From the electrochemical study, it is found that the LUMO energy level for the beta-trifluoromethylporphycene is 1.24 V more stabilized compared to that for etioporphyrin. Moreover, the deprotonation of the inner N[bond]H proton in the porphycene was observed upon the addition of DBU.