Porphyrinoid framework embedded with polycyclic aromatic hydrocarbons: new synthetic marvels

The highly conjugated tetrapyrrolic porphyrin macrocycle and its contracted and expanded congeners have been extensively used for a wide range of applications across diverse research domains because of their captivating and intriguing features. Over the years, the porphyrin framework and electronic properties of porphyrinoids have been modified and tuned by replacing one or more pyrrole ring(s) with five- and six-membered heterocycles/carbacycles, and their resulting properties have been explored. In recent times, polycyclic aromatic hydrocarbons (PAHs), such as biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, fluorene, pyrene and dibenzo[g,p]chrysene, have been used to replace one or more pyrrole rings of porphyrinoids, and resulting polycyclic-aromatic-embedded porphyrinoids show unique features that differ from those of other modified porphyrinoids. The polycyclic aromatic hydrocarbons in the porphyrinoid macrocyclic framework induce different π-conjugation pathways in macrocycles, exhibit variable degrees of aromaticity from nonaromatic to aromatic and antiaromatic and provide a unique ligand environment to form stable coordination and organometallic complexes in which metals show uncommon oxidation states and unusual reactivity. This review presents an overview of the synthesis, coordination chemistry, structure and properties of various porphyrinoids with an embedded PAH that have been reported to date.