14977-07-2Relevant academic research and scientific papers
Complex formation of β-brominated tetraphenylporphyrins and metal exchange of their cadmium complexes with d-metal salts in dimethylformamide
Maltseva,Zvezdina,Chizhova,Mamardashvili, N. Zh.
, p. 102 - 109 (2016/03/12)
Complex formation of zinc and copper(II) acetates with tetraphenylporphyrin, 2-bromo-5,10,15,20-tetraphenylporphyrin, 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyrin, and 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrin in N,N-dimethylformamide has been studied. The rate constants determined in the study of the complex formation and the metal exchange reactions have been compared.
Ultrafast dynamics of meso-tetraphenylmetalloporphyrins: The role of dark states
Liang, Yu,Bradler, Maximilian,Klinger, Melanie,Schalk, Oliver,Balaban, Mihaela Carmen,Balaban, Teodor Silviu,Riedle, Eberhard,Unterreiner, Andreas-Neil
, p. 1244 - 1251 (2013/11/06)
Studying the relaxation pathways of porphyrins and related structures upon light absorption is crucial to understand the fundamental processes of light harvesting in biosystems and many applications. Herein, we show by means of transient absorption studies, following Q- and Soret-band excitation, and aba initio calculations on meso-tetraphenylporphyrinato magnesium(II) (MgTPP) and meso-tetraphenylporphyrinato cadmium(II) (CdTPP) that electronic relaxation following Soret-band excitation of porphyrins with a heavy central atom is mediated by a hitherto disregarded dark state. This accounts for an increased rate of internal conversion. The dark state originates from an orbital localized at the central nitrogen atoms and its energy continuously decreases along the series from magnesium to zinc to cadmium to below 2.75a eV for CdTPP dissolved in tetrahydrofuran. Furthermore, we are able to directly trace fast intersystem crossing in the cadmium derivative, which takes place within (110±20)a ps. Stab in the dark: By means of transient absorption studies, following Q- and Soret-band excitation, and aba initio calculations on meso- tetraphenylporphyrinato magnesium(II) (MgTPP) and meso-tetraphenylporphyrinato cadmium(II) (CdTPP), it is shown that electronic relaxation following Soret-band excitation of porphyrins with a heavy central atom is mediated by a hitherto disregarded dark state (see picture). Copyright
Specific features of the formation of zinc and cadmium complexes with tetraphenylporphine in amphiprotic media
Kononov,Trifonova,Aleksandriiskii,Burmistrov,Koifman
, p. 413 - 416 (2009/05/30)
The kinetics of the complex formation reactions of tetraphenylporphine with zinc and cadmium acetates in mixed solvents containing alcohols and inert diluents was studied by electronic absorption spectroscopy. The dependences of the rate constant on the b
Interaction of porphyrins with adenine and adenosine complexes. Effect of a metal nature
Mamardashvili,Berezin
, p. 276 - 281 (2008/10/09)
Reactions of complex formation of 5,10,15,20-tetraphenylporphine (H 2TPP) and tetra-tert-butylphthalocyanine (H2(t-Bu) 4Pc) with adenine and adenosine complexes of d-metals in DMSO and ethanol are studied. It was found that H2TPP reacts with Cu(II) and Hg(II) adeninates and adenosinates in DMSO, but does not react with Zn(II), Co(II), and Cd(II) adeninates and adenosinates (with both bridging and monodentate type of the ligand coordination). H2(t-Bu)4Pc enters the complex formation reaction with adeninates and adenosinates of all studied metals in DMSO at almost equal rates. The states of adenine and adenosine complexes of different d-metals in DMSO and ethanol are proposed on the basis of kinetic data obtained. Pleiades Publishing, Inc., 2006.
Thermophysical and structural properties of crystalline solvates of tetraphenylporphyrin and their zinc, copper and cadmium metallo-complexes
Perlovich, German L.,Zielenkiewicz, Wojciech,Kaszkur, Zbigniew,Utzig, Eva,Golubchikov, Oleg A.
, p. 163 - 171 (2008/10/09)
The results of a thermochemical and structural investigation of the process of desolvation of crystalline solvates of tetraphenylporphyrin H2TPP with o-, m-xylene; zinc(II) tetraphenylporphyrin ZnTPP with benzene, toluene, o-, m-, p-xylene; cadmium(II) tetraphenylporphyrin CdTPP and copper(II) tetraphenylporphyrin CuTPP with o-, m-xylene are reported. Thermogravimetry and differential scanning calorimetry were used to determine the stoichiometry of crystalline solvates, the energy of activation and the heat effect of the desolvation process. The lattice parameters of the unsolvated crystalline CdTPP, ZnTPP and crystalline solvates of ZnTPP with p-xylene and CuTPP with m-xylene were determined using the X-ray powder diffraction method and the algorithm of Ito. The stoichiometry 1:1 for crystalline solvates [ZnTPP+(p-xylene)1] and [CuTPP+(m-xylene)1] was observed. The values of free volume per solvent molecules Vfree defined as the difference between volume of unit cell of crystalline solvate and the sum of the volume of a unit cell of unsolvated phase of an investigated compound and Van der Waals volume of solvent molecules were calculated. The packing coefficients Kchan of the solvent molecules located in channels of the porphyrin matrix were also calculated. For ZnTPP crystalline solvates, we found the correlations between heat of desolvation and free volume per guest molecules of unit cell, as well as between the coefficient of channel packing and the temperature for which the half-lifetime of desolvation phase is equal to 60 min. A linear kinetic compensation effect for the crystalline solvates studied was found.
Solubility and Coordinating Power of Cadmium Acetate in Reactions with Porphyrins in Aqueous-organic Solvents
Golubchikov, O. A.,Kushinova, E. M.,Berezin, B. D.
, p. 61 - 63 (2007/10/02)
The solubility method has been used to investigate the equilibrium hydration of cadmium acetate in pyridine, dioxan and tetrahydrofuran at 298.15 K.It was shown that the hydration involves the acetate ion of the salt.The kinetics of the coordination reaction of cadmium acetate with tetraphenylporphin and tetra-(p-methoxy-phenyl)porphin have been studied in water-pyridine solutions.It was shown that the addition of water catalyses the reaction as a result of the formation of hydrated forms of the salt.
Kinetics of porphyrin metalation reactions in micellar media. Singlet emission studies
Hanumantha Rao,Krishnan
, p. 3538 - 3541 (2008/10/08)
The kinetics of Cu2+, Zn2+, and Cd2+ incorporation reactions into meso-tetraphenylporphyrin (H2TPP) have been studied in neutral and anionic surfactant media. Fluorescence spectroscopy employed in these investigations revealed many advantages in deriving the kinetic data. A general kinetic scheme is proposed that takes into account implicitly the influence of surfactant concentration and interphase effects on the rates of metal incorporation reactions. The enhancement of rates of porphyrin metalation reactions in micellar media relative to those found in homogeneous media is interpreted in terms of distribution of metal ions in the stern region of the micellar media. The relative rates of metal incorporation reactions in SDS micelles for different metal ions are found to follow the order Cu2+ > Zn2+ > Cd2+. On the basis of the magnitude of protonation constant (pK3) of H2TPP in SDS micelles, a mechanism similar to that proposed in homogeneous media is advanced for the metal incorporation reaction in the micellar media.
X-Ray Crystal Structure and 113Cd N.M.R. Spectrum of αβγδ-Tetraphenylporphinatocadmium(II)-Bis(dioxan) Solvate
Rodesiler, Paul F.,Griffith, Elizabeth H.,Ellis, Paul D.,Amma, Elmer L.
, p. 492 - 493 (2007/10/02)
The 113Cd Fourier transform n.m.r. spectrum of the title compound is characterized by a single resonance at ca. 422 p.p.m. deshielded from 0.1 M CdClO4 solution; its crystal structure shows an almost planar CdN4 system with only very weak axial interactions to dioxan molecules.
