Synthesis of π-extended porphyrins via intramolecular oxidative coupling.
Porphyrins fused with other aromatic units at the meso- and β-positions have recently emerged as a hot topic of research. Their synthesis typically starts with preparation of precursors via either Suzuki coupling of a meso-bromoporphyrin or mixed-aldehyde condensation, and is followed by oxidative aromatic coupling, often using high-valent metal reagents (DDQ/Sc(OTf)(3) and Fe(III) salts are among the most popular). In recent years, porphyrins were oxidatively coupled not only with well-known aromatic hydrocarbons such as naphthalene and pyrene, but also with more complex heterocyclic fragments, including indole, phenanthro[1,10,9,8-cdefg]carbazole and BODIPY. A subtle relationship exists between the output of intramolecular oxidative coupling and the nature of the second aromatic moiety, cation in the porphyrin cavity, oxidant, and type of remaining meso-substituent. The extension of the porphyrin chromophore leads to significant change in linear and non-linear optical properties. Very strong bathochromic shifts of absorption (λ(max) reaching 1.5-2 microns in some cases) and increases in two-photon absorption cross-sections are typical for these functional dyes.
Institute of Organic Chemistry Polish Academy of Sciences, Kasprzaka 44/52 01-224, Warsaw, Poland.
Jan P
JP
Lewtak
Daniel T
DT
Gryko
D000873:Anthracenes / Q000138:chemical synthesis / Q000737:chemistry; D006841:Hydrocarbons, Aromatic / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D058451:Oxidative Coupling; D010569:Perylene / Q000138:chemical synthesis / Q000737:chemistry; D011166:Porphyrins / Q000138:chemical synthesis* / Q000737:chemistry; D011721:Pyrenes / Q000138:chemical synthesis / Q000737:chemistry
D000873:Anthracenes; D006841:Hydrocarbons, Aromatic; D011166:Porphyrins; D011721:Pyrenes; D010569:Perylene; C030984:pyrene; C034020:anthracene