Adducts of free-base meso-tetraarylporphyrins with trihaloacetic acids: Structure and photostability

Abstract Four diverse meso-tetraarylporphyrins in the form of diprotonated adducts with trifluoro-, trichloro-, tribromoacetic acids and acetic acid were investigated in benzene solution. Despite similar structural distortion of the chromophore system due to protonation, the respective adducts demonstrated different photostability when exposed to UV irradiation. The trifluoro- and trichloroacetic adducts, and the acetic acid one, showed some common features both molecular and in the mechanism of photodegradation. However, the tribromo-derivative decayed according to a different kinetic scheme, revealing a considerable impact of the bromine atoms upon the pyrrole units of the porphyrin macro…

Azoxybenzene rearrangement catalyzed by solid acids

Abstract For the first time, the potential of acidic cation-exchange resin (sulfonated polystyrene) to catalyze the Wallach rearrangement of azoxybenzene into 4-hydroxyazobenzene has been proved. This finding reveals an alternative reaction path possible in a heterogeneous process using solid acids and may help to clear some doubts concerning the rearrangement mechanism postulated so far. The resin-induced reaction was found to proceed exclusively in a non-polar medium. Reasonable yield was obtained particularly in isooctane due to favorable distribution of azoxybenzene throughout the resin's matrix. On the contrary, the HY type zeolite did not activate the rearrangement, most probably beca…

Molecular balance forms of indium phthalocyanines in benzene and pyridine solution

Abstract The electronic absorption spectra of In2Pc3, InPc2 and InPcI solid compounds after dissolvation in one of the most commonly used solvents, i.e.: benzene and pyridine have been measured. In benzene, the molecules of the diindium tripledecker phthalocyanine, In2Pc3, undergoes transformation to ionic couples [InPc]+[InPc2]-, whereas when the InPc2 compound is dissolvated, the molecules of the indium sandwiches, InPc2, remain relatively stable in the solvent. When the In2Pc3 compound is dissolvated in py, the inner Pc(2-) ring of diindium tripledecker phthalocyanine molecule undergoes disjunction and rejection. In the results of it in the solution the couple of chromophores, being in t…

The effect of organic solvents on selected microorganisms and model liposome membrane

The effect of methanol, ethanol, acetone, N,N-dimethylformamide (DMF), dimethyl sulfoxide and Nujol on the growth of Escherichia coli DH5α, Bacillus subtilis and Saccharomyces cerevisiae D273 was investigated. All of the tested cultures appeared susceptible to the organic media they were treated with, which evinced in apparent hindering of cell development. The observed diverse solvent tolerance, except from their different biochemical activity, may also be related to the changes in cell membrane fluidity induced by the solvent species. Parallel electron paramagnetic resonance investigations using egg yolk lecithin model liposomes revealed that the fluidity of the phospholipid system in cel…

Liposomes modified by mono- and bis-phthalocyanines: A comprehensive EPR study.

The impact of selected metallophthalocyanines, featuring diverse molecular structure, upon the fluidity of liposome membranes was studied using the spin label EPR technique. The “mono”-type MPc’s (M = Zn, Sn; Pc = C32H16N8 is the phthalocyanine ligand) and sandwich LnPc2 complexes (Ln = Nd, Sm, Gd) were explored. Liposomes were obtained in a sonication process, from egg yolk lecithin (EYL) in water. TEMPO and 16-DOXYL spin labels were used to monitor the peripheral and central part of the lipid double layer, respectively, which allowed to localize the phthalocyanine additive within the bilayer, as well as to perform independent measurements of changes in fluidity upon addition thereof. All …

Structural and Molecular Characterization of meso-Substituted Zinc Porphyrins: A DFT Supported Study

Structural parameters of a range of over 100 meso-substituted zinc porphyrins were reviewed and compared to show how far the nature of the functional group may affect the interatomic distances and bond angles within the porphyrin core. It was proved that even despite evident deformations of the molecular structure, involving twisting of the porphyrin's central plane, the coupled π-bonding system remains flexible and stable. DFT calculations were applied to a number of selected porphyrins representative for the reviewed compounds to emphasize the relevance of theoretical methods in structural investigations of complex macrocyclic molecular systems. Experimental and DFT-simulated IR spectral …

Sulfur Dioxide Oxidation Catalyzed by Photosensitized Ytterbium Diphthalocyanine

Oxidation of SO2 into SO3 was found effectively catalyzed by photosensitized ytterbium diphthalocyanine, YbPc2 (Pc = phthalocyanine ligand, C32H16N8) when performed in air-saturated dimethylformamide (DMF) solution at 20 °C. The process follows according to a multi-step complex mechanism involving chemical induction as its driving force. Excitation energy of the sandwich molecular system in YbPc2 is used to promote the reaction by creating a reactive intermediate form of the ytterbium complex hosting up to eight SO2 molecules. The conversion of SO2 proved complete.

Comparison of the photocatalytic degradation of 2-propanol in gas–solid and liquid–solid systems by using TiO2–LnPc2 hybrid powders

Photocatalytic degradation of 2-propanol was carried out as a probe reaction both in gas–solid and in liquid–solid systems in the presence of TiO2 both bare and impregnated with lanthanide (Sm, Gd, Ho) bis-phthalocyanines (LnPc2) used as sensitizers. Continuous and batch photo-reactors, irradiated with an equal flux of photons, were used in gas–solid and in liquid–solid systems, respectively. Propanone and acetaldehyde were the main intermediates found in both systems during 2-propanol oxidation, whereas carbon dioxide and water were the final oxidation products exclusively in the gas–solid regime. The photocatalysts exhibited significantly higher activity in the liquid–solid system than in…

Photocatalytic activity of nano and microcrystalline TiO2 hybrid systems involving phthalocyanine or porphyrin sensitizers

Hybrid photocatalysts based on TiO(2)-anatase matrix, representing the both micro- and nano-structures, impregnated with selected lanthanide diphthalocyanine and metalloporphyrin sensitizers, were compared to evaluate their activity and effectiveness in a water suspension catalytic system designed to degrade 4-nitrophenol (4-NP) in a UV-stimulated reaction. Either type of the anatase catalyst was proved to be effective in mineralizing of 4-NP. However, kinetic studies confirmed that the composite's efficiency basically depends on the nature of the macromolecular sensitizer and to a minor extent on the dimensions (micro/nano) of the TiO(2) particles. The apparent higher activity observed for…

Novel Lipophilic Lanthanide Bis-Phthalocyanines Functionalized by Pentadecylphenoxy Groups: Synthesis, Characterization and UV-Photostability

Novel sandwich-type phthalocyanines containing a rare earth metal core (Pr, Nd, Eu-Lu) and macrocycles peripherally substituted by pentadecylphenoxy groups were synthesized using a cardanol-based phthalonitrile precursor and the respective lanthanide acetate. Additionally, the metal free-base analog compound was studied for comparison. The purified reaction products were all found to be thick and viscous substances at room temperature, showing liquid crystalline behavior with a distinct increase in fluidity at ca. 40 ° C. The complexes are readily soluble in chloroalkyl solvents and dissolve fairly well in DMF with some tendency to form aggregates. Besides they are strongly hydrophobic and …

Deduction of the oxidation degree of the group A15 elements at the phthalocyanines on the basis of the Q band

meso-Aryl-substituted free-base porphyrins: formation, structure and photostability of diprotonated species

Susceptibility to interact with trifluoroacetic acid (TFA) of selected free-base porphyrins, including a novel lipophilic 3-n-pentadecyl(phenoxy)-ethoxy-phenyl-substituted porphyrin, and photostability of their diprotonated compounds was explored in benzene and N,N-dimethylformamide (DMF). Results have been discussed in terms of the commonly applied pK a -based procedure and confronted with a simple approach derived from experimentally-determined correlations reflecting the porphyrins affinity for TFA. Density functional theory (DFT) has proved the porphyrin moiety creates stable diprotonated species involving two TFA molecules, in which the fluorine atoms effectively contribute to the over…

Semiconductor @ sensitizer composites for enhanced photoinduced processes

Abstract This Chapter provides an overview of common procedures used for the preparation, characterization, and exploration of photocatalytic properties of composite materials based on inorganic semiconductors in combination with sensitizers, such as porphyrins, phthalocyanines, and related macrocyclic compounds as promoters of photoinduced processes. In this context the advantage of hybrid photocatalysts, obtained by impregnation of photosensitizers onto the surface of different semiconductors, designed for improving a choice of diverse reactions has been demonstrated, highlighting innovative aspects that contribute to better sustainability of the photocatalytic processes. Mechanistic deta…

Porphyrin and phthalocyanine photosensitizers designed for targeted photodynamic therapy of colorectal cancer

Colorectal cancer is of particular concern due to its high mortality rate count. Recent investigations on targeted phototherapy involving novel photosensitizers and drug-delivery systems have provided promising results and realistic prospects for a successful medical treatment. New research trends have been focused particularly on development of advanced molecular systems offering effective photoactive species which could be selectively delivered directly into the affected cells. Porphyrins and phthalocyanines have been considered extremely attractive for this purpose due to their molecular versatility, excellent photochemical properties and multifunctional nature. In this review it has bee…

The impact of TiO2 modifications on the effectiveness of photocatalytic processes [review]

This paper outlines the recent studies on the application of photocatalysis using semiconductors, with modified titanium dioxide (TiO2) in the process of reducing chemical contamination of surface and ground waters. During the last forty years, an increasing interest in catalysts of this type is noticeable. Hence, a wide range of methods of TiO2 modifications have been proposed so far by using its various polymorphs, composites with metals and non-metals and polymer-coatings or impregnating it with dyes that effectively absorb sunlight.

Hydrogen bond-mediated conjugates involving lanthanide diphthalocyanines and trifluoroacetic acid (Lnpc2@TFA): Structure, photoactivity, and stability

The interaction between lanthanide diphthalocyanine complexes, LnPc2 (Ln = Nd, Sm, Eu, Gd, Yb, Lu

Activity of phthalocyanine-sensitized TiO2-anatase in photooxidation of sulfite ions

Abstract Hybrid catalysts based on the TiO2 matrix impregnated with Nd, Eu and Yb diphthalocyanines proved effective in oxidation of sulfite ions under irradiation with light from the UV-visible range. Micro- and nano-crystalline anatase powders were used in preparation of the photocatalysts, which were applied in the form of a suspension in the water phase. The reaction yield was found to depend on the phthalocyanine sensitizer used and the conditions of TiO2 impregnation. The best results were obtained when micro-anatase impregnated with Yb-diphthalocyanine was used.

TiO2-based photocatalysts impregnated with metallo-porphyrins employed for degradation of 4-nitrophenol in aqueous solutions: role of metal and macrocycle

Photodegradation of organic compounds in water solutions by means of economically advantageous and environment-friendly processes is a topic of growing interest. In recent years a great attention has been devoted to TiO2-based photocatalysts for the oxidative degradation of various organic pollutants. In this context, we have prepared new photo-catalytic polycrystalline TiO2 systems impregnated with sensitizers, i.e., copper, iron or manganese porphyrins, and investigated their photoactivity for 4-nitrophenol oxidation compared with that of bare TiO2. A significant improvement of the photoreactivity was observed in the case of TiO2 impregnated with copper porphyrin, while only a slight bene…

Hybrid TiO2 @ phthalocyanine catalysts in photooxidation of 4-nitrophenol: Effect of the matrix and sensitizer type

Abstract Microcrystalline and nanocrystalline anatase (TiO2) based hybrid photocatalysts including selected phthalocyanine sensitizers were explored in photooxidation of 4-nitrophenol (4-NP) in water. Composites obtained with the homemade pure nano-anatase displayed a very poor catalytic performance compared to the other ones prepared from the commercial Tioxide-Huntsman (micro) and Evonik P25 (nano) products. In particular, the microcrystalline anatase impregnated with sandwich phthalocyanines of Gd or Yb showed excellent results both in photooxidation of 4-NP and hydroquinone, and proved the only ones which completely removed these two compounds from the system during the same reaction cy…

Investigation of phthalocyanine crystals exposed to NO2 ambient gas

Crystals of free base phthalocyanine (H2pc) and its unsubstituted metal derivatives Mpc (where M=Ni, Cu, Zn, Pb, and pc=C32H16N8 2−=phthalocyanine ligand) were examined after being exposed to NO2 ambient gas. Scanning electron microscopy (SEM) supported by X-ray microprobe analysis (EDAX), UV–Vis and FTIR spectroscopy as well as X-ray powder diffractometry (XRD) were applied to study the crystals chemistry and surface morphology. The NO2 molecules were found to penetrate the crystal unit which led to the breakdown of the phthalocyanine macrocycle. The surface of the doped crystals has been scaled and covered by a layer composed predominantly of phthalimide. Despite vacuum desorption, it has…

Effect of air-absorbed oxygen and moisture on the chemical stability of photoexcitedMg,ZnandEuphthalocyanines in dimethylformamide

Absorption of oxygen and moisture from air by MPc-DMF systems was studied and related to the molecular stability demonstrated by phthalocyanine complexes (unsubstituted MPc's : MgPc , ZnPc and EuPc2; Pc = phthalocyanine ligand, C32H16N8) subjected to UV irradiation. A lower stability of air-exposed dimethylformamide solutions is observed and is due to a specific affinity for molecular oxygen revealed by the Pc macrocycle. SEM results proved oxygen molecules fixed to the phthalocyanine solids by forces strong enough to sustain desorption under vacuum. Absorption curves determined for MPc-DMF systems also indicate oxygen accommodated by the phthalocyanine moiety. This explains the predominant…

Examples of UV–Vis profiles use as tool for evidence of the metallophthalocyanines transformation

Abstract The UV–Vis spectra for a set of MPcs (Mmetal, Pc = phthalocyanine ligand), i.e.: In(III)PcI (1), Hf(IV)PcI2Pht (Pht = phthalonitrile) (2), Sn(II)Pc (3), Sn(IV)PcI2 (4), and Ge(IV)PcI2 (5) have been examined in two solvents, O-donative acetylacetone, and non-coordinative benzene. The UV–Vis spectra in Hacac solution of 1,2 and 4,5 shows that the axially ligated iodine atoms are replaced by (acac)− anions of the solvent, whereas in 3 the oxygen donors of the solvent causing the auto-oxidation of Sn(II) to Sn(IV) ions and as a result the Sn(II)Pc is transformed into the Sn(IV)Pc(acac)2. The chloride complexes of the 1–5 compounds are formed at Hacac solution after acidification by hyd…

UV photostability of metal phthalocyanines in organic solvents

Kinetic studies of photochemical reactions induced by UV radiation in solutions of metal phthalocyanines have been carried out to determine the factors which might have influenced the stability of photosensitized phthalocyanines. Complexes of the molecular type Mpc, M'(2)pc, and Lnpc(2) (where M = Li, Mg, Fe, Co, Zn, Pb; M'= Tl; Ln = rare earth; pc = phthalocyanine ligand, C(32)H(16)N(8)(2-)) were investigated in DMF, DMSO, and pyridine. Progressive decay of the phthalocyanine macrocycle due to absorption of UV light was observed. Phthalimide found in the final photolysis product may indicate some chemically bonded oxygen involved in the solid phthalocyanine material. Fluorescence lifetimes…