A study on the aromaticity and magnetic properties of N-confused porphyrins

Abstract

In this paper, topological resonance energy (TRE) methods were used to describe the global aromaticity of nitrogen confused porphyrin (NCP) isomers. The TRE results show that all NCP isomers exhibit lower aromaticity than the normal porphyrins, and their aromaticity decreases as the number of confused pyrrole rings in the molecule increases. In the NCPs, global aromaticity decreases as the distance between the nitrogen atoms increases. The bond resonance energy (BRE) and circuit resonance energy (CRE) indices were applied to study local aromaticity and conjugated pathways. Both the BRE and CRE indices revealed that individual pyrrolic subunits maintain their strong aromatic character and are the main source of global aromaticity. Ring currents (RC) were analysed using the Hückel–London model. RC results revealed that the macrocyclic electron conjugation pathway is the main source of diatropicity. As the number of confused pyrrole rings in the molecule increases, its diatropicity gradually decreases. In the confused pyrrole rings of the NCP isomers, the diatropic RC passing through the β -positions is always weaker than that passing through the inner sections. This is unrelated to the location of the protonated or non-protonated nitrogen atom at the periphery of the molecule and must be ascribed to the unique properties of the confused pyrrole rings.

Electronic properties and redox chemistry ofN-confused metalloporphyrins

“…[5] The first N-confused porphyrin (NCP) (see Scheme 1) was synthesized in 1994. [6,7] Two of its tautomers were later successfully isolated depending on the solvent: NCP-3H and NCP-2H, [8] which, in conjunction with DFT [9] calculations, allowed for the study of their individual properties, [10][11][12] unraveling their promise for application such as the development of new photodynamic therapeutics. [13] NCP-3H exhibited a higher degree of aromaticity and was thus considered to be more stable.…”

Creation from Confusion and Fusion in the Porphyrin World─The Last Three Decades of N-Confused Porphyrinoid Chemistry

“…Notably, the combination of confusion and NH tautomerism offers a rich pool of π-conjugated macrocyclic compounds, all of which could provide unique coordination environments for metal centers. The resulting pool of porphyrinoids continues to stimulate the interest of theoretical chemists, and a large number of theoretical calculations about their structures, electronic states, and photophysical properties were conducted, offering many profound insights into porphyrin chemistry. − …”