14640-21-2Relevant academic research and scientific papers
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.
Types of interaction of meso-tetraphenylporphyrin with alkali and alkaline-earth metal ions
Chaudhuri, Tandrima,Banerjee, Manas,Ghosh, Ayan,Pan, Animesh,Ganguly Neogi, Soumya
, p. 747 - 753 (2011)
The cavity in a porphyrin can accommodate metal ions through electron donor-acceptor (EDA) interaction in acetonitrile media without any specially designed fabrication with the porphyrin subunit. Alkali metal ion forms a complex with meso-tetraphenylporphyrin (TP) in 2:1 stoichiometry, while the bivalent Mg2+ ion follows a 1:1 stoichiometry. A fluorescence interaction study indicated that TP can behave like a chemosensor for these ions present in the blood electrolytes. Specifically, for the alkali metal ions intensity-based sensing was observed, due to inhibition of photoinduced electron transfer (PET), entailing enhancement of fluorescence intensity, and for the alkaline-earth Mg2+ a mixed quenching was observed. Na+ and K+ ions can be differentiated depending upon the extent of fluorescence enhancement. Copyright
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
Effect of five membered versus six membered meso-substituents on structure and electronic properties of Mg(II) porphyrins: A combined experimental and theoretical study
Ghosh, Avijit,Mobin, Shaikh M.,Froehlich, Roland,Butcher, Ray J.,Maity, Dilip K.,Ravikanth, Mangalampalli
, p. 8287 - 8297 (2010)
Meso-tetrasubstituted Mg(II) porphyrins containing six membered phenyl groups (MgTPP) and five membered thienyl (MgTThP) and furyl groups (MgTFP) were synthesized and structurally characterized, and the effects of meso-substituents on electronic properties were studied using NMR, absorption, fluorescence spectroscopy, and electrochemical studies. Density functional theory (DFT) calculations were carried out to correlate with experimental observations. The three Mg(II) porphyrins MgTPP, MgTThP, and MgTFP were crystallized as hexa-coordinate systems with Mg(II) ion in the center of the porphyrin plane and having two tetrahydrofuran molecules as axial ligands. The X-ray studies clearly showed that the meso-furyl groups adopt a conformation in which they are more in-plane with the porphyrin plane whereas the thienyl and phenyl groups prefer an orthogonal arrangement with respect to the porphyrin plane. This arrangement of meso-substituents with the porphyrin plane helps in the enhancement of porphyrin π-delocalization in MgTFP compared to MgTThP and MgTPP. The differences in their structures are clearly reflected in their spectral and electrochemical properties. The absorption and fluorescence bands experienced bathochromic shifts on moving from six membered phenyls to five membered thienyl and furyl group, and the maximum effects were observed for meso-tetrafuryl Mg(II) porphyrin. The electrochemical studies indicated that the gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) decreases as we move from six membered phenyl groups to five membered thienyl and furyl groups, which explains the bathochromic shifts observed in absorption and fluorescence bands. Results on structure and electronic properties based on DFT studies are in agreement with experimental observations.
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.
Observations on the Mechanochemical Insertion of Zinc(II), Copper(II), Magnesium(II), and Select Other Metal(II) Ions into Porphyrins
Atoyebi, Adewole O.,Brückner, Christian
supporting information, p. 9631 - 9642 (2019/03/26)
Building on a proof of concept study that showed the possibility of the mechanochemical insertion of some M(II) metals into meso-tetraphenylporphyrin using a ball mill as an alternative to traditional solution-based methods, we present here a detailed study of the influence of the many experimental variables on the reaction outcome performed in a planetary mill. Using primarily the mechanochemical zinc, copper, and magnesium insertion reactions, the scope and limits of the type of porphyrins (electron-rich or electron-poor meso-tetraarylporphyrins, synthetic or naturally occurring octaalkylporphyrins, and meso-triphenylcorrole) and metal ion sources suitable for this metal insertion modality were determined. We demonstrate the influence of the experimental metal insertion parameters, such as ball mill speed and reaction time, and investigated the often surprising roles of a variety of grinding agents. Also, the mechanochemical reaction conditions that remove zinc from a zinc porphyrin complex or exchange it for copper were studied. Using some standardized conditions, we also screened the feasibility of a number of other metal(II) insertion reactions (VO, Ni, Fe, Co, Ag, Cd, Pd, Pt, Pb). The underlying factors determining the rates of the insertion reactions were found to be complex and not always readily predictable. Some findings of fundamental significance for the mechanistic understanding of the mechanochemical insertion of metal ions into porphyrins are highlighted. Particularly the mechanochemical insertion of Mg(II) is a mild alternative to established solution methods. The work provides a baseline from which the practitioner may start to evaluate the mechanochemical metal insertion into porphyrins using a planetary ball mill.
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.
Four aryl metal porphyrin process for the continuous production of
-
Paragraph 0065-0069, (2016/12/12)
The invention discloses a continuous production process of tetraaryl metal porphyrin. The process is as follows: firstly, adding a solvent into a multi-phase reaction separation synchronous reactor, wherein the reactor comprises a stirring reaction tower with a reflux device, and at least two constant-temperature settling towers communicated with the bottom of the stirring reaction tower, and the stirring reaction tower comprises a gas-phase region and a reaction region; during reaction, filling the solvent in the reaction region and the constant-temperature settling towers, adding the reaction material tetraaryl porphyrin and a metal salt into the stirring reaction tower for stirring when a temperature is increased to reach a reflux temperature of the solvent or reacting under the condition of ventilating air, directly settling the tetraaryl metal porphyrin generated by the reaction under gravity action to enter the constant-temperature settling towers until the constant-temperature settling tower is filled up with the tetraaryl metal porphyrin, switching the stirring reaction tower to communicate with the other constant-temperature settling tower filled with the solvent and carrying out the process alternatively to realize continuous production. The continuous production process disclosed by the invention can continuously produce high-purity tetraaryl metal porphin with high yield and low cost.
Two-photon oxygen sensing with quantum dot-porphyrin conjugates
Lemon, Christopher M.,Karnas, Elizabeth,Bawendi, Moungi G.,Nocera, Daniel G.
, p. 10394 - 10406 (2013/10/01)
Supramolecular assemblies of a quantum dot (QD) associated to palladium(II) porphyrins have been developed to detect oxygen (pO2) in organic solvents. Palladium porphyrins are sensitive in the 0-160 Torr range, making them ideal phosphors for i
The doubly oxidized, antiaromatic tetraphenylporphyrin complex [Li(TPP)][BF4]
Cissell, Julie A.,Vaid, Thomas P.,Yap, Glenn P. A.
, p. 2401 - 2404 (2007/10/03)
Oxidation of dilithium tetraphenylporphyrin, Li2(TPP), yields the doubly oxidized porphyrin complex [Li(TPP)][BF4]. Free TPP appears to be unstable. The crystal structure of [Li(TPP)][BF4] reveals that the 16-atom C-N inner ring of the porphyrin consists of alternating single and double bonds. NMR spectroscopy and nucleus-independent chemical shift (NICS) calculations, in addition to the distortion from planarity observed in the crystal structure, indicate that the 16 π-electron inner C-N ring of the porphyrin is antiaromatic.
