625080-10-6Relevant articles and documents
Synthesis and characterization of meso-to-meso directly linked porphyrin-diazaporphyrin triads
Jia, Yingying,Xu, Ling,Yin, Bangshao,Zhou, Mingbo,Song, Jianxin
, p. 814 - 820 (2018)
Beginning with 5,10,15-triarylporphyrin-nickel complex, five meso-to-meso directly linked porphyrin-diazaporphyrin triads were successfully prepared for the first time through a series of reactions including formylation via Vilsmeier-Haack reaction, condensation with pyrrole, bromination with N-Bromosuccinimide (NBS), oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), metallated cyclization of dibromodipyrrin-metal complexes with NaN3 and demetalization. All these triads were comprehensively characterized by 1H NMR, high-resolution mass spectrometry and UV-vis absorption. In addition, the structure of compound 6Ni was unambiguously determined by X-ray diffraction analysis, which showed that the two dihedral angles are both 86.65 (4)° between each mean plane of porphyrin and that of central diazaporphyrin The UV-vis absorption spectra disclosed that the longest wavelengths of Soret bands and Q bands for these triads were observed at 429 and 642 nm, respectively. In contrast to diazaporphyrin-porphyrin dyads, diazaporphyrin dimers and diazaporphyrin monomers reported previously the molar extinction coefficients, particularly for triad 8Ni are much higher.
Efficient synthesis and versatile reactivity of porphyrinyl grignard reagents
Fujimoto, Keisuke,Yorimitsu, Hideki,Osuka, Atsuhiro
, p. 4327 - 4334 (2014/07/21)
Iodine-magnesium exchange between iodoporphyrins and iPrMgCl·LiCl proceeded successfully without decomposition of the porphyrin core. The resulting porphyrinyl Grignard reagents are nucleophilic enough to react with various carbonyl compounds, such as ald
Ultrafast photodynamics of exciplex formation and photoinduced electron transfer in porphyrin-fullerene dyads linked at close proximity
Tkachenko, Nikolai V.,Lemmetyinen, Helge,Sonoda, Junko,Ohkubo, Kei,Sato, Tomoo,Imahori, Hiroshi,Fukuzumi, Shunichi
, p. 8834 - 8844 (2007/10/03)
The ultrafast photodynamics of porphyrin-fullerene dyads in which the distance between the porphyrin and C60 moieties is varied systematically at close proximity has been examined using fluorescence up-conversion and pump-probe transient absorption techniques with time resolutions of ca. 100 fs. The porphyrin-fullerene dyads examined are MP-D-C60 (M = Zn and 2H) in which the C60 moiety is directly connected with the porphyrin ring at the meso position and MP-O-C60, MP-M-C60, and MP-P-C60 in which the C60 moiety is linked with porphyrin moieties through the benzene ring at the ortho, meta, and para positions, respectively. The charge transfer (CT) bands are observed for MP-D-C60 and MP-O-C60, whereas no CT band is seen or MP-M-C60 and MP-P-C60. Time-resolved absorption spectral measurements indicate that the photoexcitation of ZnP-D-C60 in benzonitrile (PhCN) results in formation of the exciplex, which decays to the ground state without forming the charge-separated state. The strong interaction between the ZnP and the C60 moieties due to the short linkage distance in ZnP-D-C60 as indicated by the observation of the strongest CT band at the ground state results in formation of the exciplex. The energy of the exciplex is lower than that of the charge-separated state even in a polar solvent such as PhCN. In contrast, the photoexcitation of the dyad with longer linkage, ZnP-O-C60, in PhCN results in formation of the charge-separated state via the exciplex formation, which is higher in energy than the charge-separated state. The photodynamics of exciplex formation of porphyrin-C60-linked dyads with a short linkage is characterized by the extremely fast formation rate from the singlet excited states of porphyrins involving both the second and first excited states due to the interaction between the porphyrin and C60 moieties, which are placed at close proximity. In the case of MP-D-C60, the exciplex formation from the first singlet excited state of MP occurs at an ultrafast time scale with a time constant of 160 fs and that from the second singlet excited state occurs faster with a time constant less than 50 fs.
