Aromaticity and photophysical properties of various topology-controlled expanded porphyrins

Recently, expanded porphyrins have come to the forefront in the research field of aromaticity, and been recognized as the most appropriate molecular system to study both Hückel and MÖbius aromaticity because their molecular topologies can be easily changed and controlled by various methods. Along with this advantage, many efforts have been devoted to the exploration of the aromaticity–molecular topology relationship based on electronic structures in expanded porphyrins so that further insight into the aromaticity – a very attractive field for chemists – can be provided. In this tutorial review, we describe the recent developments of various topology-controlled expanded porphyrins and their photophysical properties, in conjunction with the topological transformation between Hückel and MÖbius aromaticity by various conformational control methods, such as synthetic methods, temperature control, and protonation.