208346-07-0Relevant articles and documents
Synthesis and Dissociation Kinetics of Zinc, Copper, Cobalt, and Manganese Complexes with 2,3,7,8,12,18-Hexamethyl-5-phenyl-13,17-diethylporphin and Its Nitro-Substituted Analogs in Proton-Donor Media
Kuvshinova,Bykova,Vershinina,Gornukhina,Semeikin
, p. 736 - 740 (2019)
Nitro-substituted 2,3,7,7,8,12,18-hexamethyl-5-phenyl-13,17-diethylporphins with nitro groups in positions 10 and 20 of the porphyrin core and in the para-position of the benzene ring have been synthesized. The structure of the obtained compounds has been confirmed by H1 NMR, UV, and IR spectroscopy as well as mass spectrometry. The kinetics of dissociation of zinc, copper, cobalt, and manganese complexes of the obtained porphyrins in proton-donor media has been studied. The stability of the porphyrin metal complexes has been related to the electronic effects of the substituents in the tetrapyrrole cycle and spatial distortion of the latter.
Synthesis, Electrochemical, and Photophysical Study of Covalently Linked Porphyrin Dimers with Two Different Macrocycles
Kadish, Karl M.,Guo, Ning,Van Caemelbecke, Eric,Froiio, Antonella,Paolesse, Roberto,Monti, Donato,Tagliatesta, Pietro,Boschi, Tristano,Prodi, Luca,Bolletta, Fabrizio,Zaccheroni, Nelsi
, p. 2358 - 2365 (2008/10/08)
Four unsymmetrical covalently linked porphyrin dimers were synthesized, and their electrochemical, spectroelectrochemical, and/or photophysical properties were examined. The investigated compounds are represented as M[p-(TPP-DEHMP)]M and M[m-(TPP-DEHMP)]M (M = H2, Zn), where p-(TPP-DEHMP) is the tetraanion of 1-[5-(10,15,20-triphenylporphyrinyl)]-4-[10-(2,18-diethyl-3,7,8,12,13,17- hexamethylporphyrinyl)]benzene and m-(TPP-DEHMP) is the tetraanion of 1-[5-(10,15,20-triphenylporphyrinyl)]-3-[10-(2,18-diethyl-3,7,8,12,13,17- hexamethylporphyriny)]benzene. The oxidation and reduction potentials of Zn[p-(TPP-DEHMP)]Zn are virtually identical to combined oxidation and reduction potentials of (TPP)Zn and (OEP)Zn, i.e., cyclic voltammograms of the heterodimers resemble those of the superposed monomeric units under the same experimental conditions. The UV-visible spectra of neutral, singly oxidized, and/or singly reduced Zn[p-(TPP-DEHMP)]Zn also resemble superposed spectra of the respective neutral, oxidized, or reduced monomeric (TPP)Zn and (OEP)Zn derivatives. Hence, both the electrochemical and spectroelectrochemical data suggest that there is little electronic interaction between the two subunits of the heterodimers in their neutral, singly oxidized, or singly reduced forms. The photophysical properties of four related homoleptic dimers, M[p-(TPP-TPP)]M and M[m-(TPP-TPP)]M, where M = H2 or Zn, p-(TPP-TPP) = the tetraanion of 1, 4-bis[5-(10,15,20-triphenylporphyrinyl)]benzene, and m-(TPP-TPP) = the tetraanion of 1,3-bis[5-(10,15,20-triphenylporphyrinyl)]benzene, were also examined, and their data were compared to the data for the above heteroleptic dimers. Irradiation of H2[p-(TPP-DEHMP)]H2 and M[m-(TPP-DEHMP)]M (M = H2, Zn) with excitation wavelengths in the visible spectrum of the DEHMP subunit, results in an efficient energy transfer between the DEHMP and TPP moieties. Calculated energy transfer rate constants agree well with the experimental data and suggest that the energy transfer processes are best described by a Foester mechanism. H2[p-(TPP-DEHMP)]H2 and H2[m-(TPP-DEHMP)]H2 thus demonstrate highly efficient and directional energy transfer processes rather than charge separation between the two subunits after irradiation.
