Unique Role of Heterole-Fused Structures in Aromaticity and Physicochemical Properties of 7,8-Dehydropurpurins.

ABSTRACT

Porphyrins with a fused five-membered ring, such as 7,8-dehydropurpurins, have appeared as an emerging class of unique porphyrinoids. Their altered absorption spectra, relatively short lifetimes of excited states, and small HOMO-LUMO gaps arise from the harmony of the antiaromatic 20π-circuit and the aromatic 18π-circuit. In this regard, the electronic properties of 7,8-dehydropurpurins are expected to be controlled by modulating the contribution of the antiaromatic π-circuit to the whole aromaticity. Here the comparison of pyrrole- and phosphole-fused 7,8-dehydropurpurins is reported in terms of their aromaticity and physicochemical properties. The spectroscopic investigation revealed the larger contribution of the antiaromatic 24π-circuit in pyrrole-fused 7,8-dehyrdopurpurins than in phosphole-fused 7,8-dehydropurpurins. The DFT calculations also supported the feasibility of tuning the aromaticity of 7,8-dehydropurpurins by heterole-fused structures. Thus, the introduction of heterole-fused structures into porphyrinoids is a universal strategy to get new insight into aromaticity and their intrinsic properties in cyclic π-conjugated molecules.