This review focuses on the postfunctionalization of porphyrins and related compounds through catalytic and stoichiometric organometallic methodologies. The employment of organometallic reactions has become common in porphyrin synthesis. Palladium-catalyzed cross-coupling reactions are now standard techniques for constructing carbon-carbon bonds in porphyrin synthesis. In addition, iridium- or palladium-catalyzed direct C-H functionalization of porphyrins is emerging as an efficient way to install various substituents onto porphyrins. Furthermore, the copper-mediated Huisgen cycloaddition reaction has become a frequent strategy to incorporate porphyrin units into functional molecules. The use of these organometallic techniques, along with the traditional porphyrin synthesis, now allows chemists to construct a wide range of highly elaborated and complex porphyrin architectures.

Curved π-conjugated molecules have attracted considerable interest because of the unique properties originating from their curved π surface. However, the synthesis of such distorted molecules requires harsh conditions, which hamper easy access to heteroatom-containing curved π systems. Here we report the synthesis of a π-extended azacorannulene with nitrogen in its centre. The oxidation of 9-aminophenanthrene provides tetrabenzocarbazole, which is converted to the azabuckybowl through palladium-catalysed intramolecular coupling. The electron-donating nature and curved π surface of the azabuckybowl enable its tight association with C60 in solution and solid states. High charge mobility is observed for the azabuckybowl/C60 assembly. This compound may be of interest in the fields of curved π systems as fullerene hosts, anisotropic π donors and precursors to nitrogen-containing nanocarbon materials.

Directly linked corrole dimer 1, which has a planar cyclooctatetraene in its core, has been synthesized from 2-borylcorrole in excellent yield. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) oxidation of 1 provides its oxidized form 4, which has two NH protons in each corrole core. Dicorrole 4 and its Zn(II) complex 6 exhibit broad electronic absorption spectra, and magnetic measurement has revealed their biradicaloid character.