Structurally well-defined conjugated meso-aminoporphyrin oligomers analogous to polyanilines.

Polyaniline, which is formed by the oxidative polymerization of aniline, is a widely explored conducting polymer with several stable oxidation states, and can be applied in advanced materials, including sensing devices and electrochemical catalysts. The marriage of polyanilines with the diverse chemistry of porphyrins is expected to confer new properties, including a combination of electrical, optical, magnetic and chemical properties. Herein, we demonstrate that meso-aminodiarylporphyrin, a porphyrin analogue of aniline, undergoes oxidative oligomerization in an acidic solution under an oxygen atmosphere to yield stable oligomeric products that are analogous to fully oxidized polyanilines. The so-formed oligomers are composed of the same number of electron-rich porphyrinoid and electron-deficient quinoid moieties, and they exhibit a broad electronic absorption band in the near infrared (NIR) region, which is attributable to intramolecular charge transfer (ICT) transition from electron-rich porphyrinoid moieties to electron-deficient quinoid ones. The quinoid moieties in the oligomers could be reversibly reduced using sodium ascorbate to obtain all-porphyrinoid oligomers that resemble fully reduced polyanilines. The fully reduced oligomers do not exhibit the NIR ICT band. Furthermore, three types of partially reduced tetramers consisting of a single quinoid moiety were also obtained, among which two interconverted in solution. Their interconversion was significantly accelerated in the presence of a protic solvent. This result is consistent with the high electron conductivity of partially oxidized polyanilines following their protonation.

Metal-Free Synthesis of meso-Aminoporphyrins through Reduction of meso-Azidoporphyrins Generated in Situ by Nucleophilic Substitution Reactions of meso-Bromoporphyrins.

A facile and metal-free method for the preparation of free base meso-aminodiarylporphyrins from readily available meso-bromodiarylporphyrins is described. Simple treatment of meso-bromoporphyrins with sodium azide and sodium ascorbate in DMF affords the corresponding meso-aminoporphyrins in very good yields. This method involves the aromatic nucleophilic substitution (SNAr) of a bromo group with an azido group and the subsequent in situ reduction of the introduced azido group by sodium ascorbate. This amination reaction can be scaled up to gram scale without any decrease of the product yield. The amination reaction of free base meso-dibromoporphyrin affords a monoaminated product selectively, whereas that of the Ni(II) complex furnishes a diaminated product that is oxidized by air under ambient conditions but isolable as a trifluoroacetyl ester. Metal-insertion reactions of the obtained free base aminoporphyrins afford the corresponding metal complexes (Ni(II), Cu(II), Zn(II), and Pd(II)) all in good yields except the Pd(II) complex. Synthetic methods for the preparation of N-mono- or dialkylaminoporphyrins from the free base meso-aminoporphyrins have been also established.