Novel triazaporphyrins were synthesized using 1,9-dibromodipyrromethene as a key starting material. These triazaporphyrins exhibit comparatively intense Soret and Q bands in the UV/vis region due to their hybrid properties between porphyrins and phthalocyanines.

A novel triphyrin was unexpectedly formed as a major by-product in the synthesis of meso-aryl-substituted dibenzo-5,10,15-triazaporphyrin from meso-aryl-substituted 1,9-dibromodipyrromethene and 5,6-diaryl-substituted 1,3-diiminoisoindoline in the presence of N,N-dimethylaminoethanol (DMAE). X-ray single crystal diffraction analysis elucidated that the terminal α-positions of this triphyrin were bridged by an N-methylaminoethoxy chain, which plausibly originated from DMAE during the reaction. The same compound was also obtained as a major product in the reaction of DMAE and meso-aryl-substituted 1,9-dibromodipyrromethene. Its unique properties, such as conformational flexibility of the bridging moiety and broad absorption in the visible region, were also revealed by 1 H NMR and UV-vis absorption spectroscopies.

Despite significant interest, the chiroptical properties of subporphyrins have rarely been investigated because chiral subporphyrins are elusive. Here, inherently chiral subporphyrins are elaborated by forming a fused pyran ring at the periphery of an A2B-type meso-aryl-substituted subporphyrin. Their circular dichroism (CD) properties are largely affected by the peripheral substituents and the dihedral angles between the meso-aryl substituents and the subporphyrin core: the β-perbromo subporphyrin with an orthogonal arrangement of the meso-phenyl substituents to the subporphyrin core exhibits weak CD signals corresponding to the Q bands, whereas the unsubstituted species with smaller dihedral angles shows relatively intense CD signals. A detailed structure–property relationship of these chiral subporphyrins was elucidated by time-dependent (TD) DFT calculations. This study reveals that the CD properties of chiral subporphyrins can be controlled by peripheral substitution and meso-aryl substituents.

An ether cleavage reaction of A2B-type subporphyrin bearing an ortho-anisyl substituent afforded a phenolate-bridged dimer. A head-to-tail structure of the dimer was unambiguously elucidated by single crystal X-ray diffraction analysis. UV-vis absorption and magnetic circular dichroism spectra indicated a minor interaction between the subporphyrin chromophores. Density functional theory calculations provided a detailed insight into the electronic structures of the subporphyrin dimer.