Porphyrin 2 was hydrolyzed to amine-porphyrin 3.
Many artificial assemblies incorporate porphyrin derivatives as light receptors in solar energy conversion, which takes place in the spectral sensitization of wide band gap semiconductors [3-5].
Porphyrins Phthalocyanines 1998, 2, 123.
NCP has a same backbone structure as porphyrin(1,1,1,1). However, NCP possesses a "confused pyrrole", which is a pyrrolic moiety connected to the surrounding -carbons at the - and -positions. Owing to this unusual linkage, the positions of pyrrolic NH and -CH are switched. As a result, NCP contains an NNNC core and an outward pointing N atom. When a metal is coordinated in the core, a kind of organometallic complex having a carbon-metal bond, is formed. On the other hand, the peripheral nitrogen atom serves as a hydrogen bonding donor/acceptor as well as a metal coordination site.
NCP derivatives other than -tetraaryl-type are continuously synthesized (, ). NCP framework is composed of four pyrrolic rings just like standard porphyrins, but the X-ray structure analyses have shown that the pyrrole ring is tilted by ca. 30 degree to the NCP mean plane, which is a marked contrast to those of porphyrins with high symmetry and planarity (). Reflecting the structural difference, the tautomerism of NCP differs largely from that of normal porphyrin. NCP tautomerism involves the peripheral nitrogen as well as inner nitrogen atoms, and two kinds of tautomers are observed by the spectroscopic methods. One type of tautomer has three hydrogen atoms in the core (NCP-3H), and the other has two hydrogen atoms in the core and one hydrogen atom at the peripheral nitrogen (NCP-2H). The both structures were elucidated by X-ray diffraction analyses. NCP-3H is dominantly observed in the nonpolar solvents, whereas NCP-2H is highly stabilized in polar solvents, such as DMF and acetone, by the hydrogen bonding interaction at the periphery NH moiety. These two tautomers show different aromaticity, photochemical properties, and so on.
Tetraphenylporphyrin - Wikipedia
In 1994, Furuta and Latos-Grazynski's groups independently reported a new type of porphyrin isomer, N-confused porphyrin (NCP) or inverted porphyrin.
the porphyrinogen is subsequent oxidized to delivers the porphyrin.
In the present work we are interested in the synthesis of porphyrin dyad 9 and 10, in which the porphyrin moiety is attached to C60 by an amide bond.
Synthesis of a Porphyrin and its Metal Complex
The proposed dyads request the synthesis of -substituted porphyrins bearing a phenyl group substituted with the functional group to make the link and three identical substituted phenyl groups (AB3-porphyrin).
Porphyrins | Porphyrin | Biochemistry
Porphyrins are being used as platforms for the study of theoretical principles, as catalysts, as drugs, as electronic devices, and as spectroscopic probes in biology and medicine.
7/23/2011 · Porphyrin
Owing to the existence of the confused pyrrolic ring, NCP possesses high reactivity compared to the porphyrin. For example, electrophilic substitution reactions (nitrarion, bromination, etc.) readily occur at -CH position of the confused pyrrolic ring (, , ) and the -CH moiety is easily oxidized to form an amide-NCP in the presence of SnCl2, O2 and H2O (). Furthermore, treating NCP with Cu(II) in the presence of O2, the confused pyrrole ring was removed to afford a tripyrrinone ().
Synthesis of Porphyrin Dimers Fused with a Benzene …
The Porphyrin Handbook represents a timely publication dealing with the recent chemistry, physics, biology, and medicine of porphyrins and related macrocycles.
organic chemistry: Introduction Synthesis of Porphyrins
Dibromo-NCP, which is obtained by bromination of NCP, can be converted into N-fused porphyrin (NFP), via inversion of the pyrrole and subsequent nucleophilic substitution of the adjacent pyrrolic nitrogen. Additionally, some kinds of nucleophiles (e.g., ROï¼) attack the fused moiety of NFP and force the ring-opening to rebirth the NCP. NFP exhibits characteristic electro- and photochemical properties, such as NIR absorption and emission (). Apart from dibromo-NCP route, NFP skeleton can be synthesized directly by a treatment of NCP with Re2CO10 ().