Littérature scientifique sur le sujet « Tetra phenyl porphyrins »

The incorporation of the five following porphyrins: meso-tetra(4-phenyl)porphyrin (TPP); meso-tetra(4-sulfonato-phenyl)porphyrin (TPPS4); meso-tetra(4-naphthyl)porphyrin (TNP); tri-sulfo-tetra-phenyl porphyrin (TPPS3) and tetra-sulfonato-naphthyl porphyrin (TNPS4) into human blood cells was investigated using flow cytometry, and absorption and emission spectroscopy. The percentage of stained cells, measured in a fluorescence cytometer, provided information on the efficiency of incorporation of fluorescent dye molecules into different types of cells. The yield of the incorporation of a dye was dependent on the type of dye and the solvent used for cell incubation. The degree of dye aggregation and ionization varied with the incubation medium, but dye molecules incorporated into cells seemed to be restricted to those in the monomeric state, exhibiting similar fluorescence yield. Of the three sulfonated porphyrins investigated only TPPS4 was efficiently incorporated into leukocytes. In the incubation solvent, this dye was in monomeric and neutral form. TPPS3 which was also in monomeric form, practically was not incorporated into cells. TPP and TNP dissolved in 5% aqueous dimethyl sulfoxide were present mostly in aggregated forms but they penetrated the cells with a high efficiency.

The crystallization and the crystal and molecular structure of a very slightly soluble electrostatically interacting pair of porphyrins is described. The tetra-anion 5,10,15,20-tetrakis-(4-sulfonatophenyl)-21,23H-porphyrin [H2TPPSO3][Formula: see text] and the tetra-cation 5,10,15,20-tetra([Formula: see text]-methylpyridyl)21H,23H-porphyrin [H2TMePyP][Formula: see text] are found to form an alternating one-dimensional stack that is stabilized by electrostatic interactions between the porphyrin rings but also by [Formula: see text] interactions between all substituted phenyl rings in the ensemble. The resulting interactions between the porphyrins is exceptionally tight.

One of the most important but undesirable properties of the porphyrins is their oxidative photodegradation which can occur in non-polar solvents, under irradiation, and in the presence of molecular oxygen. The mechanism of this oxidative photodegradation implies singlet oxygen and different radical species. This paper is concerned with the mechanism of the photodegradation of some meso-tetra(4-X-phenyl)porphyrins(TXPP) and meso-tetra(4-X-1-naphtyl)porphyrins(TXNP), where X could have different organic structures (-NH2,-N02,-S03H,-OH,-OCH3,-CH3). Based on different spectral methods (UV-Vis and IR absorption spectroscopy, emission spectroscopy, X-ray diffraction, electronic microscopy, and mass spectrometry, we propose a photodegradation mechanism, and we evaluated the effect of some scavengers (2,6-di-tert-butyl-phenol (DTBF) for radical species, 1,3-diphenylisobenzofuran (DPBF) for singlet oxygen and nitro-blue tetrazolium (NBT) for superoxide anion) during the porphyrin photodegradation.

Continuous proliferation of bacteria in a wound delays its healing process, and could further extend to becoming a chronic wound infection. The effectiveness of different porphyrins as a photosensitizer in antibacterial photodynamic therapy for the inactivation of some wound-colonizing bacteria was studied as a screening experiment. Meso-tetra(4-methoxyphenyl) porphyrin, (TMPP), meso-tetra(4-hydroxyphenyl) porphyrin (THPP), meso-tetra(4-carboxyphenyl) porphyrin, (TCPP), meso-tetra(N-methyl-4-pyridyl) porphyrin, (TMPyP) were synthesized, each complexed with zinc, tin and silver. The in-vitro and photo-toxicity properties of the porphyrins and their complexes were assessed on some selected wound colonizing multi-drug resistant bacterial strains (Staphylococcus aureus, Klebsiella pneumoniae, Proteus mirabilis, and Escherichia coli) using agar well diffusion method. Photo-toxicity of the compounds were investigated using a 100-Watt tungsten lamp while the in-vitro toxicity was carried out in the dark. The results were compared with previously reported work carried out by this group on meso-tetra(phenyl)porphyrin (TPP), meso-tetra(4-sulphonatophenyl) porphyrin, (TPPS) and their corresponding Zn, Sn and Ag complexes. Most of the porphyrins showed biocidal activities against three of the test isolates with an exception to Proteus sp. ZnTMPyP and ZnTHPP only showed photo-toxic activities against the four test isolates. While SnTHPP, ZnTPPS, ZnTCPP, and SnTCPP all exhibited both toxic and photo-toxic activities against all four bacterial isolates. The Ag-porphyrins had the poorest inactivation activity.

A reaction between 5,10,15,20-tetra(4-hydroxyphenyl)porphyrin and 1-bromopyrene resulted in the formation of 5,10,15,20-tetra[4-(4-(pyrenyl-1)butoxy)phenyl]porphyrin (1), while cross-condensation between 4-(4-(pyrenyl-1)butoxy)benzaldehyde, ferrocenecaboxaldehyde, and pyrrole resulted in the formation of 5-ferrocenyl-10,15,20-tri[4-(4-(pyrenyl-1)butoxy)phenyl]porphyrin (2), 5,10-diferrocenyl-15,20-di[4-(4-(pyrenyl-1)butoxy)phenyl]porphyrin (3), and 5,15-diferrocenyl-10,20-di[4-(4-(pyrenyl-1)butoxy)phenyl]porphyrin (4). All pyrene-containing porphyrins were characterized by 1H NMR, UV-vis, MCD, and high-resolution ESI methods, while their electronic structures and the nature of the excited states were elucidated using density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. The molecular structure of 1 and its fluorescence quenching upon the addition of C[Formula: see text] fullerene was also investigated using X-ray crystallography and steady-state fluorescence approaches.

Mn (III)-tetra phenyl porphyrin-acetate (MnTPPOAc) and some kinds of meso-phenyl substituted porphyrins by hydroxyl groups and their Mn (III) complexes were synthesized. These Mn -porphyrins were used as catalyst in the epoxidation of various alkenes with tetra-n-butylammonium hydrogen monopersulfate (n- Bu4NHSO5 ) as oxidant and tetra-n-butylammonium acetate (n- Bu4NOAc ) as the axial ligand. The following order of catalytic activity was observed for cyclooctene: T(2,3-OHP)PMnOAc ≫ T(2,4,6-OHP)PMnOAc ≥ T(4-OHP)PMnOAc ≥ T(2,6-OHP)PMnOAc ≥ TPPMnOAc and T(2,3-OHP)PMnOAc ≫ TPPMnOAc > T(4-OHP)PMnOAc > T(2,4,6-OHP)PMnOAc > T(2,6-OHP)PMnOAc for other alkenes. Different activity and stability of the catalysts were interpreted based on the hydrogen bonding between hydroxyl groups with appropriate orientation on the meso-position of the phenyl groups and axial bases or oxidant. T(2,3-OHP)PMnOAc catalyst has shown optimal condition for effective hydrogen bonding. In the case of other catalysts, electronic and steric factors overcome the hydrogen bonding effect.

Soret-excited resonance Raman (RR) spectra are reported for some 40 nonplanar metalloporphyrin complexes. These include (i) copper β-octabromo-meso-tetra(para-X-phenyl)porphyrins, Cu [ Br 8 T (p- X - P ) P ] ( X = CH 3, H , F , CF 3, NO 2); (ii) copper β-octachloro-meso-tetra(para-X-phenyl)porphyrins, Cu [ Cl 8 T (p- X - P ) P ] ( X = H , CF 3); (iii) zinc β-octabromo-meso-tetraphenylporphyrin, Zn [ Br 8 TPP ], and zinc β-octasubstituted meso-tetrakis(pentafluorophenyl)porphyrins, Zn [ Y 8 TPFPP ] ( Y = CH 3, Cl , Br ); (iv) nickel β-octabromo-meso-tetra(para-X-phenyl)porphyrins, Ni [ Br 8 T (p- X - P ) P ] ( X = CH 3, H , F , Br , COOMe , CF 3, NO 2), with and without bis-ligated axial pyridine and imidazole ligands; (v) nickel β-octachloro-meso-tetra(para-X-phenyl)porphyrins, Ni [ Cl 8 T (p- X - P ) P ] ( X = CH 3, H , F , COOMe , CF 3, NO 2), again with and without bis-ligated axial pyridine ligands; and (vi) nickel octaethyltetraphenylporphyrin, Ni [ OETPP ], and palladium octaethyltetraphenylporphyrin, Pd [ OETPP ]. The spectra lead to the following conclusions. For a particular nonplanar porphyrin ligand, the high-frequency RR marker bands ν2 and ν4 downshift with increasing size of the coordinated metal ion, including a low- to high-spin transition for nickel porphyrins. In contrast, for a particular coordinated metal ion, these frequencies downshift with increasing nonplanarity of the porphyrin ligand, which in turn correlates with decreasing metal–nitrogen distances or the 'core size'. Similar results were also found for β-octaalkyl-meso-tetraphenylmetalloporphyrins by Shelnutt and coworkers. Thus, it appears that this complicated multiple-valued core size dependence of the high-frequency RR marker bands may be a generally shared property of all saddled metalloporphyrins. Variations in the electronic character of the metalloporphyrins resulting from variations in the para-substituents on meso-aryl groups do not result in significant shifts in the RR marker bands. The symmetric C meso – C phenyl stretching frequency (ν1) at approximately 1240 cm-1 is prominent in all the RR spectra except those of the low-spin Ni saddled porphyrins, for which they are relatively suppressed, and possible electronic-structural implications of this effect are discussed. In the low-frequency regions of the RR spectra of the compounds studied, the strongest band is roughly around 300 cm-1 and appears to be relatively safely assignable as γ16, a pyrrole tilting mode that strongly resembles the saddling mode in terms of atomic displacements.

The two-photon absorption (TPA) properties of two newly synthesized substituted porphyrins: 5,10,15,20-tetra-(4-pyrrolidinylphenyl)porphyrin (1) and 5,10,15,20-tetra-(4-diphenylamino-benzoic acid phenyl) porphyrin ester (3) were measured by the femtosecond Z-scan technique at 800 nm Ti : sapphire laser and by direct nonlinear optical transmission (NLT) using nanosecond Nd : YAG laser. The substituent effects, pumped wavelength and the environment upon the molecular TPA cross-section were investigated. It is found that the TPA cross-section for 3 is enhanced under excitation of 800 nm, relative to its precursor, 5,10,15,20-tetra(4-hydroxyphenyl) porphyrin (2), due to the former possessing extension conjugation of "D-A-core-A-D" molecular architecture. Also sample 3 obtained an increased TPA cross-section in rigid film relative to that in solution, suggesting that the enhancement is facilitated by the quasi-planar structure which allows direct interbranch conjugation throughout the molecule.

Aldehydes with bulky substituents in the ortho-positions have been historically difficult in porphyrin synthesis, presumably owing to steric hindrance around the reactive site. We have used mechanochemistry for the simple, room-temperature synthesis of tetra-meso-substituted porphyrins. In the present study, mesitaldehyde undergoes acid-catalyzed mechanochemical condensation with pyrrole to give meso-tetrakis[2,4,6-(trimethyl)phenyl]porphyrin (TMP) after oxidation in solution. Yields are similar to those obtained using high-temperature porphyrin synthesis, although they remain significantly lower than some optimized room-temperature, solution-based methods. Yields of the mechanochemical synthesis were found to increase slightly upon longer exposure to an organic oxidizing agent in solution. This indicates that the mechanochemical condensation step may be more successful than initially realized. This work shows that mechanochemistry is a successful, simple, room-temperature method for producing tetra-meso-substituted porphyrins with bulky substituents.

High valent Mn(O) species of a series of electron-rich and -deficient meso-tetra(aryl)porphyrins (aryl = phenyl, 2-Cl-phenyl, 2-nitrophenyl, 2-Me-phenyl, 2-Br-phenyl, 2,6-di-Cl-phenyl 4-OMe-phenyl, 4-Me-phenyl, 4-Cl-phenyl and 4-pyridyl) were prepared at 273 K.

2013/2014
Traditional semiconductor technology will reach a size limit within the next few years. A possible solution could be the use of organic molecules in technological applications as single functional units in metal-organic based devices; the success of this approach strongly depends on the understanding of the behaviour of these molecules on metallic surfaces. The interaction with metallic substrates and the interaction between the molecules themselves determine the electronic and magnetic properties of the system, and it is thus of fundamental interest to study these metal-organic interfaces both in the case of single molecules and layer structures. In this thesis, an extensive study of the electronic and magnetic properties of tetra-phenyl-porphyrin (2H-TPP) molecules adsorbed on metal surfaces is reported. By means of scanning tunnelling microscopy (STM) we studied the adsorption geometry of these molecules on the Au(111), Ag(111) and Cu(100) surfaces. By using X-ray photoemission spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, a temperature-induced conformational adaptation reaction of the 2H-TPP molecules adsorbed on the Au(111) and Ag(111) surfaces, upon annealing at 550 K, is described. A possible dehydrogenation reaction, with the formation of new C-C bonds, could explain the rotation of the molecule phenyl rings parallel to the surface plane and the associated increasing in the molecule-substrate interaction. In-situ metalation of porphyrins in ultra-high vacuum is obtained by two methods: in the first one, the metalation of 2H-TPP on Ag(111) is achieved by direct metal evaporation (Mn, Rh and Fe) on the molecular layer; in the second case we report the self-metalation of 2H-TPP through the coordination with a metal atom from the Fe(110) and Al(111) substrates. In addition, we investigated the effects of metalation and temperature-induced conformational adaptation on the molecule-substrate interaction, by means of XPS and NEXAFS, in the case of CoTPP on Ag(111). The magnetic properties resulting from the metal coordination are studied by X-ray magnetic circular dichroism (XMCD). Here, a description of the magnetic coupling of a MnTPPCl single layer with a Fe(110) ferromagnetic substrate is disclosed. Moreover, we focused on the study of the magnetic properties and exchange coupling of two layer of molecule and a ferromagnetic thin film. In the case of a MnTPP layer on FeTPP/Fe(110) the magnetic coupling extends to the second layer of molecules, for which the magnetization is opposite with respect to the substrate.
Le tradizionali tecnologie utilizzate nell’industria dei semiconduttori raggiungeranno, entro breve tempo, il limite nella miniaturizzazione dei loro componenti. Una possibile alternativa potrebbe venire dall’utilizzo di molecole organiche come singole unità funzionali in dispositivi metallo-organici; d’altra parte il successo di questo approccio dipende in maniera sostanziale dalla comprensione del comportamento di queste molecole sulle superfici dei metalli. L’interazione con il substrato metallico e la stessa interazione tra le molecole determinano le proprietà elettroniche e magnetiche di questi sistemi, ed è dunque di fondamentale interesse lo studio di queste interfacce metallo-organiche sia nel caso di singole molecole che di strutture più complesse. In questa tesi è riportato uno studio dettagliato delle proprietà elettroniche e magnetiche di tetra-fenil-porfirine (2H-TPP) adsorbite su superfici metalliche. Attraverso la microscopia a scansione a effetto tunnel (STM) è stata studiata la geometria di adsorbimento di queste molecole sulle superfici Au(111), Ag(111) e Cu(100). Utilizzando le spettroscopie XPS (X-ray photoemission spectroscopy) e NEXAFS (near-edge X-ray absorption fine structure) è descritta la reazione di adattamento conformazionale delle 2H-TPP adsorbite sulle superfici Au(111) e Ag(111) a seguito del processo di annealing a 550 K. Una possibile reazione di de-idrogenazione, con la formazione di nuovi legami C-C, può spiegare la rotazione dei gruppi fenili della molecola verso la superficie e l’aumento dell’interazione molecola-substrato ad esso associato. La metallazione in-situ delle porfirine in ultra-alto vuoto è ottenuta in due modi: nel primo, la metallazione delle 2H-TPP su Ag(111) è raggiunta con la diretta evaporazione del metallo (Mn, Rh e Fe) sullo strato di molecole; nel secondo caso, sulle superfici Fe(110) e Al(111) la metallazione avviene automaticamente tramite la coordinazione della 2H-TPP con un atomo della superficie. Inoltre, gli effetti della metallazione e dell’adattamento conformazionale sull’interazione molecola-substrato sono stati studiati, tramite XPS e NEXAFS, nel caso di CoTPP su Ag(111). Le proprietà magnetiche risultanti dalla coordinazione della molecola con un atomo metallico sono state studiate per mezzo della tecnica XMCD (X-ray magnetic circular dichroism). In particolare, viene descritto l’accoppiamento magnetico di un singolo strato di MnTPPCl con un substrato ferromagnetico Fe(110). Inoltre, ci si è focalizzati sullo studio delle proprietà magnetiche tra due strati di molecole e un film sottile ferromagnetico. Nel caso specifico di MnTPP su FeTPP/Fe(110) l’accoppiamento magnetico si estende al secondo strato di molecole, per il quale la magnetizzazione è opposta rispetto al substrato.
XXVII Ciclo
1986

Cette thèse est une étude théorique sur la interface de porphyrine de cobalt avec des surfaces métalliques avec le code VASP DFT. Le cadre DFT nécessaire a été introduit dans le chapitre 1. La structure de la jBardeen, une programme ecrit en Java, pour la simulation de la STM est expliqué dans le chapitre 2 et le code source est jointe en annexe. Une étude de l'adsorption de CoTPP sur les surfaces métalliques a été entrepris dans le chapitre 3. Différents paramètres de calcul ont été évalués: Le site d'adsorption et de la géométrie à la fois la molécule et la surface ont été étudiés par rapport à la xc-fonctionnel et correction de la dispersion utilisée. Une adsorption site le plus stable est identifié. Par conséquent, ce site plus stable a été étudiée pour sa structure électronique. Calculés images STM avec le code jBardeen ont été comparés avec une experimentation de CoTPP Cu sur une surface (111) avec une couverture sous monocouche. Dans le chapitre 4, un adatome Fe a été présenté à la CoTPP sur Ag système (111). Trois sites de liaison symétrique différentes pour l'atome Fe ont été identifiés sur le macrocycle, marqué les , bi-, brd- et bru-positions. Un moment magnétique pouvait être attestée qui a été principalement situé sur l'atome Fe. Voies possibles entre les quatre, symétriquement équivalentes, sites bi- ont été étudiées avec des méthodes différentes. Simples calculs dans le vacuum et calculs de la “Nudged Elastic Band” (NEB) de l'ensemble du système a révélé une hauteur de barrière légèrement au-dessus de 0,2 eV allant de position bi à la posititon brd. Une analyse de vibration a montré que la commutation de l'atome Fe est susceptible, lorsqu'il est perturbé hors d'équilibre dans les positions brd et bru
This thesis is a theoretical study on the cobalt porphyrin - coinage metal surface interface with the DFT code VASP. The necessary DFT framework has been introduced in chapter 1. The structure of the Java program jBardeen for STM simulation is explained in chapter 2 and the source code is attached as Appendix. A study of the adsorption of CoTPP on coinage metal surfaces has been undertaken in chapter 3. Different parameters of the calculation have been evaluated: the adsorption site and the geometry of both the molecule and surface have been investigated with respect to the xc-functional and dispersion correction used. A most stable adsorption site -bridge down- is identified. Consequently, this most stable site was investigated for its electronic structure. Calculated STM images with the jBardeen code were compared with an experiment of CoTPP on a Cu(111) surface with sub monolayer coverage. In chapter 4 an Fe adatom was introduced to the CoTPP on Ag(111) system. Three symmetrically different binding sites for the Fe atom were identified on the macrocycle, labelled the bi-, brd- and bru-positions for bisector, bridge down and bridge up respectively. A magnetic moment could be evidenced which was mainly located on the Fe atom. Possible pathways between the four symmetrically equivalent bisector sites were investigated with different methods. Single point calculations in vacuum and Nudged Elastic Band (NEB) of the whole system revealed a barrier height of slightly above 0.2 eV going from bi- to the brd-position. A vibrational analysis showed that switching of the Fe atom is likely, when perturbed out of equilibrium in the brd- and bru- positions