14640-21-2Relevant articles and documents
Synthesis, molecular structure, spectroscopic characterization and antibacterial activity of the pyrazine magnesium porphyrin coordination polymer
Khelifa, Arbia Ben,Ezzayani, Khaireddine,Guergueb, Mouhieddinne,Loiseau, Frederique,Saint-Aman, Eric,Nasri, Habib
, (2021)
A new material of magnesium(II) polymer compound with the formula {[MgII(TPP)(pz)]? 0.5[MgII(TPP)]?CH2Cl2}n (I), (TPP) = meso?tetraphenylporphyrinato and pz = pyrazine) was synthetized and characterized by IR, UV-visible, PL photoluminescence and 1H NMR spectroscopy studies, single-crystal XRD analyses and cyclic voltammetry. The crystal structure of (I) is made by the 1D {[Mg(TPP)(pz)]} polymeric chains (molecules I(A)) where the tetracoordinated magnesium(II) complexes [Mg(TPP)] (molecules I(B)) are located as well as the dichloromethane solvent molecules. The crystal packing of (I) is stabilized by intermolecular C[sbnd]H?Cg π interactions where Cg is the centroid of phenyl and pyrrole rings. Additionally, the photophysical properties have been evaluated by UV-visible absorption and fluorescence emission spectroscopies. The UV-visible spectrum of (I) shows a redshift Soret band value (428 nm) compared to that of the free base H2TPP porphyrin while the λmax values of the Q bands are in the range 560 – 610 nm. The optical gap of (I) was estimated at 1.99 eV. The cyclic voltammogram of the title compound presents two reversible oxidation waves and one reversible reduction wave. The HOMO and LUMO energy values were deduced from the voltammogram which are -4.96 and -2.85 eV respectively. Furthermore, bioactivity investigations revealed that the free porphyrin, the starting material [MgII(TPP)] and complex (I) could be used as potential antibacterial agents.
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)
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
Synthesis and photophysical properties of novel pyrene-metalloporphyrin dendritic systems
Rojas-Montoya, Sandra M.,Vonlanthen, Mireille,Porcu, Pasquale,Flores-Rojas, Gabriel,Ruiu, Andrea,Morales-Morales, David,Rivera, Ernesto
, p. 10435 - 10447 (2019/07/22)
A novel series of dendronized porphyrins bearing pyrene units in the periphery (Porph-O-Gn) and their metal complexes (M-[Porph-O-Gn]) are reported. The pyrene-containing Frechet-type dendrons up to the first generation were synthesized and further reacted with 5-phenol-10,15,20-triphenylporphyrin via an esterification reaction to afford the desired pyrene-labeled dendronized porphyrins. Later, these compounds were used as ligands to produce the corresponding complexes of Zn2+, Cu2+, Mg2+ and Mn3+. With the compounds in hand, the optical and photophysical properties of the dendritic metalloporphyrins were studied by absorption and fluorescence spectroscopy. The quantum yields, F?rster radius and efficiency of energy transfer were determined and discussed as a function of the structure and the donor-acceptor distances, finding an efficient energy transfer from the pyrene moiety to the metallated porphyrin core in each case.
Design of oxophilic metalloporphyrins: An experimental and DFT study of methanol binding
Olsson, Sandra,Dahlstrand, Christian,Gogoll, Adolf
supporting information, p. 11572 - 11585 (2018/08/28)
By systematic measurements we have evaluated a series of tetraphenyl metalloporphyrins and halogenated tetraphenyl metalloporphyrin derivatives for binding to ligands with oxygen containing functional groups, using methanol, acetic acid and acetone as examples. Experimental binding constants identified three metalloporphyrins with good binding to all three ligands: MgTPFPP, MgTPPBr8 and ZnTPPBr8 as well as a range of porphyrins binding to select ligands. Based on these results the optimal porphyrins can be selected for the desired binding interactions. We also show how to use DFT calculations to evaluate the potential binding between a metalloporphyrin and a ligand, which is deduced from free energies of binding ΔG, charge transfer ΔQ, and change of metal spin state. Computations on unsubstituted porphyrins in lieu of tetraphenyl porphyrin systems yield reliable predictions of binding interactions with good correlation to the corresponding experimental data. The calculations have also yielded interesting insights into the effect of halogenation in the β-position on the binding to ligands with oxygen containing functional groups.
