Showing papers on "Porphyrin published in 2016"
TL;DR: Mechanistic investigation reveals that the presence of single Co atoms in the MOF can greatly boost the electron-hole separation efficiency in porphyrin units, resulting in significantly enhanced photocatalytic conversion of CO2.
Abstract: Modular optimization of metal–organic frameworks (MOFs) was realized by incorporation of coordinatively unsaturated single atoms in a MOF matrix. The newly developed MOF can selectively capture and photoreduce CO2 with high efficiency under visible-light irradiation. Mechanistic investigation reveals that the presence of single Co atoms in the MOF can greatly boost the electron–hole separation efficiency in porphyrin units. Directional migration of photogenerated excitons from porphyrin to catalytic Co centers was witnessed, thereby achieving supply of long-lived electrons for the reduction of CO2 molecules adsorbed on Co centers. As a direct result, porphyrin MOF comprising atomically dispersed catalytic centers exhibits significantly enhanced photocatalytic conversion of CO2, which is equivalent to a 3.13-fold improvement in CO evolution rate (200.6 μmol g−1 h−1) and a 5.93-fold enhancement in CH4 generation rate (36.67 μmol g−1 h−1) compared to the parent MOF.
598 citations
TL;DR: In this article, a porphyrin-based porous organic polymer (POP-TPP) was synthesized from free-radical polymerization of tetrastyrylporphyrin monomer under solvothermal conditions.
213 citations
TL;DR: This review highlights and summarizes various optically active porphyrin and phthalocyanine molecules prepared using a wide range of structural modification methods to improve the design of novel structures and their applications.
Abstract: This review highlights and summarizes various optically active porphyrin and phthalocyanine molecules prepared using a wide range of structural modification methods to improve the design of novel structures and their applications. The induced chirality of some illustrative achiral bis-porphyrins with a chiral guest molecule is introduced because these systems are ideal for the identification and separation of chiral biologically active substrates. In addition, the relationship between CD signal and the absolute configuration of the molecule is analyzed through an analysis of the results of molecular modeling calculations. Possible future research directions are also discussed.
204 citations
TL;DR: In this article, a bisimidazole-functionalized porphyrin cobalt(III) complexes have been devised, synthesized and characterized using NMR, MS and elemental analysis.
140 citations
TL;DR: Results indicate that these nanoparticles exhibit stable single-crystalline and nanoporous frameworks and collective optical properties resulted from coupling of molecular porphyrins and photocatalytic activities such as photodegradation of methyl orange pollutants and hydrogen production.
Abstract: The design and engineering of the size, shape, and chemistry of photoactive building blocks enables the fabrication of functional nanoparticles for applications in light harvesting, photocatalytic synthesis, water splitting, phototherapy, and photodegradation. Here, we report the synthesis of such nanoparticles through a surfactant-assisted interfacial self-assembly process using optically active porphyrin as a functional building block. The self-assembly process relies on specific interactions such as π–π stacking and metalation (metal atoms and ligand coordination) between individual porphyrin building blocks. Depending on the kinetic conditions and type of surfactants, resulting structures exhibit well-defined one- to three-dimensional morphologies such as nanowires, nanooctahedra, and hierarchically ordered internal architectures. Specifically, electron microscopy and X-ray diffraction results indicate that these nanoparticles exhibit stable single-crystalline and nanoporous frameworks. Due to the hie...
131 citations
TL;DR: A donor-acceptor (D-A) structured porphyrin-containing conjugated polymer (PorCP) is reported for efficient PTT in vitro and in vivo, and shows effective photothermal tumor ablation in vivo.
Abstract: Conjugated polymers have been increasingly studied for photothermal therapy (PTT) because of their merits including large absorption coefficient, facile tuning of exciton energy dissipation through nonradiative decay, and good therapeutic efficacy. The high photothermal conversion efficiency (PCE) is the key to realize efficient PTT. Herein, a donor-acceptor (D-A) structured porphyrin-containing conjugated polymer (PorCP) is reported for efficient PTT in vitro and in vivo. The D-A structure introduces intramolecular charge transfer along the backbone, resulting in redshifted Q band, broadened absorption, and increased extinction coefficient as compared to the state-of-art porphyrin-based photothermal reagent. Through nanoencapsulation, the dense packing of a large number of PorCP molecules in a single nanoparticle (NP) leads to favorable nonradiative decay, good photostability, and high extinction coefficient of 4.23 × 104 m-1 cm-1 at 800 nm based on porphyrin molar concentration and the highest PCE of 63.8% among conjugated polymer NPs. With the aid of coloaded fluorescent conjugated polymer, the cellular uptake and distribution of the PorCP in vitro can be clearly visualized, which also shows effective photothermal tumor ablation in vitro and in vivo. This research indicates a new design route of conjugated polymer-based photothermal therapeutic materials for potential personalized theranostic nanomedicine.
130 citations
TL;DR: Electrochemical, stopped‐flow, and theoretical studies indicated that a hydride species [H‐Ni‐P] is formed by oxidative protonation of [NiP]−, which could have broad implications for the design of new exquisite cycles for H2 generation.
Abstract: A nickel(II) porphyrin Ni-P (P=porphyrin) bearing four meso-C6F5 groups to improve solubility and activity was used to explore different hydrogen-evolution-reaction (HER) mechanisms. Doubly reduced Ni-P ([Ni-P]2−) was involved in H2 production from acetic acid, whereas a singly reduced species ([Ni-P]−) initiated HER with stronger trifluoroacetic acid (TFA). High activity and stability of Ni-P were observed in catalysis, with a remarkable ic/ip value of 77 with TFA at a scan rate of 100 mV s−1 and 20 °C. Electrochemical, stopped-flow, and theoretical studies indicated that a hydride species [H-Ni-P] is formed by oxidative protonation of [Ni-P]−. Subsequent rapid bimetallic homolysis to give H2 and Ni-P is probably involved in the catalytic cycle. HER cycling through this one-electron-reduction and homolysis mechanism has been proposed previously but rarely validated. The present results could thus have broad implications for the design of new exquisite cycles for H2 generation.
127 citations
TL;DR: This work has found that free base tetraphenylporphyrin (H2TPP) is an efficient photoredox catalyst for the reaction of aldehydes with diazo compounds leading to α-alkylated derivatives.
Abstract: Metalloporphyrins not only are vital in biological systems but also are valuable catalysts in organic synthesis. On the other hand, catalytic properties of free base porphyrins have been less explored. They are mostly known as efficient photosensitizers for the generation of singlet oxygen via photoinduced energy transfer processes, but under light irradiation, they can also participate in electron transfer processes. Indeed, we have found that free base tetraphenylporphyrin (H2TPP) is an efficient photoredox catalyst for the reaction of aldehydes with diazo compounds leading to α-alkylated derivatives. The performance of a porphyrin catalyst can be optimized by tailoring various substituents at the periphery of the macrocycle at both the β and meso positions. This allows for the fine tuning of their optical and electrochemical properties and hence their catalytic activity.
125 citations
TL;DR: In this paper, the authors investigated nickel porphyrin electrocatalysts with and without an internal proton relay to elucidate the hydrogen evolution mechanism and enable the design of more effective catalysts.
Abstract: The development of more effective energy conversion processes is critical for global energy sustainability. The design of molecular electrocatalysts for the hydrogen evolution reaction is an important component of these efforts. Proton-coupled electron transfer (PCET) reactions, in which electron transfer is coupled to proton transfer, play an important role in these processes and can be enhanced by incorporating proton relays into the molecular electrocatalysts. Herein nickel porphyrin electrocatalysts with and without an internal proton relay are investigated to elucidate the hydrogen evolution mechanisms and thereby enable the design of more effective catalysts. Density functional theory calculations indicate that electrochemical reduction leads to dearomatization of the porphyrin conjugated system, thereby favoring protonation at the meso carbon of the porphyrin ring to produce a phlorin intermediate. A key step in the proposed mechanisms is a thermodynamically favorable PCET reaction composed of intramolecular electron transfer from the nickel to the porphyrin and proton transfer from a carboxylic acid hanging group or an external acid to the meso carbon of the porphyrin. The C–H bond of the active phlorin acts similarly to the more traditional metal-hydride by reacting with acid to produce H 2 . Support for the theoretically predicted mechanism is provided by the agreement between simulated and experimental cyclic voltammograms in weak and strong acid and by the detection of a phlorin intermediate through spectroelectrochemical measurements. These results suggest that phlorin species have the potential to perform unique chemistry that could prove useful in designing more effective electrocatalysts.
123 citations
TL;DR: In this article, the authors highlight porphyrinic metal-organic frameworks (porph-MOFs) assembled from metal ions and custom-designed porphrin-based bridging ligands.
Abstract: This paper highlights porphyrinic metal–organic frameworks (porph-MOFs) assembled from metal ions and custom-designed porphyrins. The contents are divided into three sections based on the types of polytopic porphyrin bridging ligands in porph-MOFs: (1) porph-MOFs containing 5,10,15,20-tetra(4-pyridyl)porphyrinato (TPyP) ligand and other pyridyl-based porphyrin bridging ligands, (2) porph-MOFs containing 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrinato (TCPP) ligand and other carboxyphenyl-based porphyrin bridging ligands, and (3) porph-MOFs containing other custom-designed porphyrin-based bridging ligands.
117 citations
TL;DR: A micelle-like hybrid natural-artificial light-harvesting nanosystem was prepared through protein-framed electrostatic self-assembly of phycocyanin and a four-armed porphyrin star polymer that can inhibit donor self-quenching effectively and display efficient transfer of excitation energy in water.
Abstract: A micelle-like hybrid natural-artificial light-harvesting nanosystem was prepared through protein-framed electrostatic self-assembly of phycocyanin and a four-armed porphyrin star polymer. The nanosystem has a special structure of pomegranate-like unimolecular micelle aggregate with one phycocyanin acceptor in the center and multiple porphyrin donors in the shell. It can inhibit donor self-quenching effectively and display efficient transfer of excitation energy (about 80.1 %) in water. Furthermore, the number of donors contributing to a single acceptor could reach as high as about 179 in this nanosystem.
TL;DR: Li et al. as mentioned in this paper constructed a pure organic heterostructure of graphitic-C3N4/(FeTPP)(2)O on the basis of the pi-pi and the Fe-amine interactions.
Abstract: Due to the two-dimensional flexible structure and abundant pendant amine, graphitic-C3N4 (g-C3N4) may be easily modified by organic molecules as a promising photocatalyst for solar H-2 production from water. Here, through a simple liquid chemical reaction between g-C3N4 and the precursor of m-oxo dimeric iron(III) porphyrin [(FeTPP)(2)O], we provide a novel route to construct a pure organic heterostructure of g-C3N4/(FeTPP)(2)O on the basis of the pi-pi and the Fe-amine interactions. The experimental results demonstrated that (FeTPP)(2)O acted not just as a photosensitizer, but also played the role of a charge promotor to prohibit the recombination of the excited electrons and holes of g-C3N4. As compared to pure or mixed g-C3N4 and/or (FeTPP)(2)O, the obtained pure organic g-C3N4/(FeTPP)(2)O heterostructure exhibited dramatic photocatalytic H-2 production under solar light without any cocatalysts.
TL;DR: Results showing that the chemical nanohybrids exhibit improved nonlinear optical properties compared to those of the benchmark material C60, and the constituent RGO or porphyrins.
Abstract: Reduced graphene oxide (RGO)-porphyrin (TPP) nanohybrids (RGO-TPP 1 and RGO-TPP 2) were prepared by two synthetic routes that involve functionalization of the RGO using diazonium salts. The microscopic structures, morphology, photophysical properties and nonlinear optical performance of the resultant RGO-TPP nanohybrids were investigated. The covalent bonding of the porphyrin-functionalized-RGO nanohybrid materials was confirmed by Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, and thermogravimetric analysis. Attachment of the porphyrin units to the surface of the RGO by diazotization significantly improves the solubility and ease of processing of these RGO-based nanohybrid materials. Ultraviolet/visible absorption and steady-state fluorescence studies indicate considerable π-π interactions and effective photo-induced electron and/or energy transfer between the porphyrin moieties and the extended π-system of RGO. The nonlinear optical properties of RGO-TPP 1 and RGO-TPP 2 were investigated by open-aperture Z-scan measurements at 532 nm with both 4 ns and 21 ps laser pulses, the results showing that the chemical nanohybrids exhibit improved nonlinear optical properties compared to those of the benchmark material C60, and the constituent RGO or porphyrins.
TL;DR: The covalent grafting of an Fe porphyrin on carbon nanotubes led to efficient electroreduction of CO2 into CO in water (pH 7.3) and CO was obtained with high selectivity and turnover at 0.5 V overpotential.
TL;DR: A diaminotriazinedecorated porphyrin-based microporous hydrogen-bonded organic framework has been successfully prepared and characterized using single crystal X-ray diffraction analysis as mentioned in this paper.
Abstract: A diaminotriazine-decorated porphyrin-based microporous hydrogen-bonded organic framework has been successfully prepared and characterized using single crystal X-ray diffraction analysis. Its activated phase exhibits permanent porosity, gas separation, and proton conductivity under humid conditions.
TL;DR: In this article, the authors demonstrate a new strategy for cooperative catalysis and proton abstraction via the incorporation of independent species competent in the desired reactivity into a metal-organic framework (MOF) thin film.
Abstract: Here, we demonstrate a new strategy for cooperative catalysis and proton abstraction via the incorporation of independent species competent in the desired reactivity into a metal–organic framework (MOF) thin film. The highly porous MOF, designated as PCN-224-Ni, is constructed by Zr–oxo nodes and nickel(II) porphyrin linkers. Films of PCN-224-Ni were grown in situ on FTO and were found to electrochemically facilitate the water oxidation reaction at near neutral pH.
TL;DR: Covalent incorporation of porphyrin in conjugated polymer backbone for development of efficient polymer-dot photosensitizer is described, revealing that the light-harvesting polymer dominantly transfer the excitation energy to the p Morphyrin unit, yielding efficient singlet oxygen generation for photodynamic therapy.
TL;DR: Insight is provided into the electronic structure, formation, and N-H insertion reactivity of an iron porphyrin carbene, a model of a complex believed to exist in an experimentally studied artificial metalloenzyme, and a possible expansion of enzymatic substrate scope, to include aliphatic amines.
Abstract: Iron porphyrin carbenes constitute a new frontier of species with considerable synthetic potential. Exquisitely engineered myoglobin and cytochrome P450 enzymes can generate these complexes and facilitate the transformations they mediate. The current work harnesses density functional theoretical methods to provide insight into the electronic structure, formation, and N–H insertion reactivity of an iron porphyrin carbene, [Fe(Por)(SCH3)(CHCO2Et)]−, a model of a complex believed to exist in an experimentally studied artificial metalloenzyme. The ground state electronic structure of the terminal form of this complex is an open-shell singlet, with two antiferromagnetically coupled electrons residing on the iron center and carbene ligand. As we shall reveal, the bonding properties of [Fe(Por)(SCH3)(CHCO2Et)]– are remarkably analogous to those of ferric heme superoxide complexes. The carbene forms by dinitrogen loss from ethyl diazoacetate. This reaction occurs preferentially through an open-shell singlet trans...
TL;DR: These azulene-containing porphyrinoids exhibit unique and complex reactivity that compares favorably with better studied p Morphyrin analogue systems, and azuliporphyrins derivatives show promise in the development of new catalytic systems.
Abstract: ConspectusFirst reported in 1997, azuliporphyrins have proven to be a truly remarkable family of porphyrin analogues. In this system, although the porphyrin framework is retained, one of the pyrrolic moieties has been replaced by an azulene unit. Azulene favors electrophilic substitution at the 1,3-positions, which are structurally analogous to the α-positions in pyrrole, and this property facilitates the construction of azulene-containing porphyrinoid systems. Azuliporphyrins were first prepared from tripyrranes and 1,3-azulenedicarbaldehyde using a “3 + 1” variant on the MacDonald reaction. Subsequently, azulenes were shown to react with acetoxymethylpyrroles under acidic conditions to generate azulitripyrranes that could be utilized in a back-to-front “3 + 1” methodology to form azuliporphyrins and related heteroporphyrinoids. In addition, the favorability of azulenes toward 1,3-substitution was applied to one-pot syntheses of tetraarylazuliporphyrins and calix[4]azulenes.Azuliporphyrins have significa...
TL;DR: MOF1 represents the first example of MOF based on 3d metal ion exhibiting visible-light-assisted reduction of nitroaromatics under mild conditions without the assistance of noble metal cocatalysts.
Abstract: A microporous Ni(II)-porphyrin metal–organic framework (MOF), [Ni3(Ni-HTCPP)2(μ2-H2O)2(H2O)4(DMF)2]·2DMF, (MOF1) (where, Ni-HTCPP = 5,10,15,20-tetrakis(4-benzoate) porphyrinato-Ni(II)) has been synthesized by the solvothermal route. Single-crystal X-ray diffraction study of 1 reveals a 2D network structure constituted by Ni3 cluster and [Ni-HTCPP]3– metalloligand having (3, 6)-connected binodal net with {43}2{46·66·83}-kgd net topology. The 2D layers are further stacked together through π–π interactions between the porphyrin linkers to generate a 3D supramolecular framework which houses 1D channels with dimension of ∼5.0 × 9.0 A2 running along the crystallographic a-axis. Visible-light-assisted photocatalytic investigation of MOF1 for heterogeneous reduction of various nitroaromatics at room temperature resulted in the corresponding amines with high yield and selectivity. On the contrary, the Ni(II)-centered porphyrin tetracarboxylic acid [Ni–H4TCPP] metalloligand does not show the photocatalytic activity...
TL;DR: This work shows that μ-nitrido-bridged diiron porphyrin and phthalocyanine complexes are highly active catalytic oxidants, which react with methane with very low reaction barriers and a rate-determining hydrogen-atom-abstraction step.
Abstract: μ-Nitrido-bridged diiron porphyrins and phthalocyanines are known to be efficient oxidants that are able to oxidize some of the strongest C–H bonds in nature, such as the one in methane. The origin of their catalytic efficiency is poorly understood, and in order to gain insight into the structural and electronic features of this chemical system, we performed a detailed and systematic study into their chemical properties and reactivities using density functional theory. Our work shows that μ-nitrido-bridged diiron porphyrins and phthalocyanines are highly active catalytic oxidants, which react with methane with very low reaction barriers and a rate-determining hydrogen-atom-abstraction step. Furthermore, the μ-nitrido-bridged diiron porphyrin and phthalocyanine complexes react with a free energy of activation that is more than 10 kcal mol–1 lower in energy than that found for cytochrome P450 Compound I, which is known to be one of the most efficient C–H hydroxylating agents in Nature. We have analyzed the ...
TL;DR: The first systematic study of cobaloxime-based hydrogen photoproduction in mixed pH 7 aqueous/acetonitrile solutions is reported and it is demonstrated that H2 evolution can be tuned through electronic modifications of the axial cobalt ligand or through introduction of TiO2 nanoparticles.
Abstract: We report on the first systematic study of cobaloxime-based hydrogen photoproduction in mixed pH 7 aqueous/acetonitrile solutions and demonstrate that H2 evolution can be tuned through electronic modifications of the axial cobalt ligand or through introduction of TiO2 nanoparticles. The photocatalytic systems consist of various cobaloxime catalysts [Co(dmgH)2(L)Cl] (L = nitrogen-based axial ligands) and a water soluble porphyrin photosensitizer. They were assayed in the presence of triethanolamine as a sacrificial electron donor. Optimal turnover numbers related to the photosensitizer are obtained with electron-rich axial ligands such as imidazole derivatives (1131 TONs with N-methyl imidazole). Lower stabilities are observed with various pyridine axial ligands (443 TONs for para-methylpyridine), especially for those containing electron-acceptor substituents. Interestingly, when L is para-carboxylatopyridine the activity of the system is increased from 40 to 223 TONs in the presence of TiO2 nanoparticles.
TL;DR: Three A–D–A porphyrin-based small molecules are employed as donors in bulky heterojunction organic solar cells and striking a delicate balance between solubility, morphology and device fabrication leads to PCEs of up to 7.7%.
Abstract: Porphyrin-based small molecules as donors have long been ignored in bulky heterojunction organic solar cells due to their unfavorable aggregation and the low charge mobility. With the aim of striking a delicate balance between molecular design, morphology, interfacial layer and device fabrication to maximize the power conversion efficiency (PCE) of organic solar cells, three comparable porphyrin-based small molecules with an acceptor–donor–acceptor configuration have been developed for use as donor materials in solution processed small molecule bulk heterojunction organic solar cells. In these molecules, electron-deficient 3-ethylrhodanine is introduced into the electron-rich porphyrin core through 5,15-bis(phenylethynyl) linkers. Structural engineering with 10,20-bis(2-hexylnonyl) aliphatic peripheral substituent on the porphyrin core, instead of the aromatic substituents such as 10,20-bis[3,5-di(dodecyloxyl)phenyl], and 10,20-bis(4-dodecyloxylphenyl), can simultaneously facilitate stronger intermolecular π–π stacking and higher charge transfer mobility in the film, leading to a maximum PCE of 7.70% in a conventional device. The inverted devices have also been demonstrated to have long-term ambient stability and a comparable PCE of 7.55%.
TL;DR: In this article, a new class of epitaxial porphyrin metal-organic framework thin films whose photophysical properties can be tuned by the introduction of electron-donating diphenylamine (DPA) groups into the skeleton was demonstrated.
Abstract: We demonstrate the fabrication of a new class of epitaxial porphyrin metal–organic framework thin films whose photophysical properties can be tuned by the introduction of electron-donating diphenylamine (DPA) groups into the porphyrin skeleton. The attachment of DPA groups results in strongly improved absorption characteristics, yielding the highest photocarrier generation efficiency reported so far. DFT calculations identify a shift of the charge localization pattern in the VBM (lowest unoccupied molecular orbital), confirming that the introduction of the DPA groups is the main reason for the shift of the optical absorption spectrum and the improved photocurrent generation.
TL;DR: A series of porous twofold interpenetrated In-CoIII (porphyrin) metal-organic frameworks (MOFs) were constructed by in situ metalation of porphyrin bridging ligands and used as efficient cooperative catalysts for the hydration of terminal alkynes, highlighting the potential application of MOFs in cooperative catalysis.
Abstract: A series of porous twofold interpenetrated In-CoIII(porphyrin) metal–organic frameworks (MOFs) were constructed by in situ metalation of porphyrin bridging ligands and used as efficient cooperative catalysts for the hydration of terminal alkynes. The twofold interpenetrating structure brings adjacent CoIII(porphyrins) in the two networks parallel to each other with a distance of about 8.8 A, an ideal distance for the simultaneous activation of both substrates in alkyne hydration reactions. As a result, the In-CoIII(porphyrin) MOFs exhibit much higher (up to 38 times) catalytic activity than either homogeneous catalysts or MOF controls with isolated CoIII(porphyrin) centers, thus highlighting the potential application of MOFs in cooperative catalysis.
TL;DR: Pb-TCPP is the first 3D porous Pb-MOF that exhibits both gas adsorption properties and electrocatalytic activity for an oxygen evolution reaction (OER).
Abstract: A 3D non-interpenetrating porous metal-organic framework [Pb2(H2TCPP)]·4DMF·H2O (Pb-TCPP) (H6TCPP = 5,10,15,20-tetra(carboxyphenyl)porphyrin) was synthesized by employment of a robust porphyrin ligand. Pb-TCPP exhibits a one-dimensional channel possessing fairly good capability of gas sorption for N2, H2, Ar, and CO2 gases, and also features selectivity for CO2 over CH4 at 298 K. Furthermore, Pb-TCPP shows electrocatalytic activity for water oxidation in alkaline solution. It is the first 3D porous Pb-MOF that exhibits both gas adsorption properties and electrocatalytic activity for an oxygen evolution reaction (OER).
TL;DR: In this article, a room-temperature solution phase reaction was developed to synthesize a covalent organic framework (COF) for the first time, which possesses a 2D chess board-like structure in the abplane and a 1D channel with an open-window size of around 1.9 nm along the c-axis in the modeled crystal structure.
Abstract: A room-temperature solution phase reaction was developed to synthesize a covalent organic framework (COF) for the first time. The synthesized azodioxy-linked porphyrin-based COF (POR-COF) possesses a 2D chess board-like structure in the ab-plane and a 1D channel with an open-window size of around 1.9 nm along the c-axis in the modeled crystal structure. The electrical conductivity of POR-COF increases by more than 3 orders of magnitude through I2 doping. The photoconductivity of the I2-doped COF material was also studied firstly. POR-COF shows interesting doping-enhanced photo-current generation.
TL;DR: In this article, the authors summarize the use of click reaction for the synthesis of porphyrin-based compounds and the reaction conditions used in each example, including the type and the place of the substrate present on the porphrin ring.
15 Jan 2016
TL;DR: The efficient singlet oxygen production of PR-TRIS-IONP together with their water solubility, points to the great promise that these new nanotools represent for PDT.
Abstract: The preparation of novel porphyrin derivatives and their immobilization onto iron oxide nanoparticles to build up suitable nanotools for potential use in photodynamic therapy (PDT) has been explored. To achieve this purpose, a zinc porphyrin derivative, ZnPR-COOH, has been synthesized, characterized at the molecular level and immobilized onto previously synthesized iron oxide nanoparticles covered with oleylamine. The novel nanosystem (ZnPR-IONP) has been thoroughly characterized by a variety of techniques such as UV-Vis absorption spectroscopy, fluorescence spectroscopy, X-ray photoloectron spectroscopy (XPS) and transmission electron microscopy (TEM). In order to probe the capability of the photosensitizer for PDT, the singlet oxygen production of both ZnPR-IONP and the free ligand ZnPR-COOH have been quantified by measuring the decay in absorption of the anthracene derivative 9,10-anthracenedipropionic acid (ADPA), showing an important increase on singlet oxygen production when the porphyrin is incorporated onto the IONP (ZnPR-IONP). On the other hand, the porphyrin derivative PR-TRIS3OH, incorporating several polar groups (TRIS), was synthesized and immobilized with the intention of obtaining water soluble nanosystems (PR-TRIS-IONP). When the singlet oxygen production ability was evaluated, the values obtained were similar to ZnPR-COOH/ZnPR-IONP, again much higher in the case of the nanoparticles PR-TRIS-IONP, with more than a twofold increase. The efficient singlet oxygen production of PR-TRIS-IONP together with their water solubility, points to the great promise that these new nanotools represent for PDT.
TL;DR: The planar π-conjugated porphyrin, zinc(II) 5,10,15,20-tetrakis[5-acetylthiopentyloxy)phenyl]porphyrin was developed to modify the interface between poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) and perovskite to improve the photovoltaic performance.
Abstract: In hybrid organic–inorganic perovskite solar cells (PSCs), interfacial engineering can efficiently improve the photovoltaic performance. In this work, the planar π-conjugated porphyrin, zinc(II) 5,10,15,20-tetrakis[5-(p-acetylthiopentyloxy)phenyl]porphyrin, was developed to modify the interface between poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) and perovskite. The modified devices increased their highest power conversion efficiency (PCE) to 14.05% relative to 11.35% for the reference devices without modification. Such enhancement in efficiency is mainly attributed to the improved open-circuit voltage (Voc) and fill factor (FF), which benefit from fast hole-extraction and low charge recombination after the employment of well-aligned interlayer.