<i>meso</i>-Aryl-Substituted Subporphyrins: Synthesis, Structures, and Large Substituent Effects on Their Electronic Properties

Two synthetic methods of meso-aryl-substituted subporphyrins have been developed by means of the reaction of pyridine−tri-N-pyrrolylborane with a series of aryl aldehydes. One method relies on the condensation under Adler conditions with chloroacetic acid in refluxing 1,2-dichlorobenzene to afford subporphyrins in 1.1−3.2%, and the other is a two-step reaction consisting of the initial treatment of the two substrates with trifluoroacetic acid at 0 °C followed by air-oxidation in refluxing 1,2-dichlorobenzene to provide subporphyrins in up to 5.6% yield. 1H NMR studies indicate that phenyl and sterically unhindered substituents at the meso position of subporphyrins rotate rather freely even at −90 °C, whereas the rotation of meso-2,4,6-trimethoxyphenyl substituents is strictly prohibited even at 130 °C. The structures of six subporphyins have been revealed by X-ray crystallographic analysis to be all cone-shaped tripyrrolic macrocycles. Dihedral angles of meso-phenyl and sterically unhindered aryl substituents to the subporphyrinic core are rather small (38.3−55.7°) compared to those of porphyrin analogues, whereas those of meso-2,4,6-trimethoxy-substituted subporphyrins are large (68.7−75.7°). These rotational features of the meso-aryl substituents lead to their large influences on the electronic properties of subporphyrins, as seen for 4-nitrophenyl-substituted subporphyrin 14e that exhibits perturbed absorption and fluorescence spectra, depending upon solvents. Large solvent-polarity dependence of the fluorescence of 14e suggests the charge-transfer character for its excited state. Electrochemical and theoretical studies are performed to understand the electronic properties. Overall, meso-aryl-substituted subporphyrins are promising chromophores in future functional devices.