Porphyrin Systems Research Articles

Meso-5,15-Bis[3-(isopropylidenegalactopyranoxy)phenyl]-10,20-bis(4-methylphenyl)porphyrin

The crystal structure of a glycosylated porphyrin (P_Gal2) system, C70H70N4O12, where two isopropylidene protected galactose moieties are attached to the meso position of a substituted tetraaryl porphyrin is reported. This structure reveals that the parent porphyrin is planar, with the galactose moieties positioned above and below the porphyrin macrocycle. This orientation likely prevents porphyrin–porphyrin H-type aggregation, potentially enhancing its efficiency as a photosensitizer in photodynamic therapy. Notable non-bonding C—H...O and C—H...π interactions among adjacent P_Gal2 systems are observed in this crystal network. Additionally, the tolyl groups of each porphyrin can engage in π–π interactions with the delocalized π-systems of neighboring porphyrins.

Visible-light Driven Unsaturated Dicarboxylate Production from Gaseous CO<sub>2</sub> and Pyruvate with the System of Water-soluble Zinc Porphyrin and Dual-biocatalysts

Visible-light Driven Unsaturated Dicarboxylate Production from Gaseous CO<sub>2</sub> and Pyruvate with the System of Water-soluble Zinc Porphyrin and Dual-biocatalysts

Recent Advances in Main Group Coordination Driven Porphyrins: A Comprehensive Review

AbstractThe novel and exciting class of porphyrin‐based compounds are the main group coordination‐driven porphyrins (MGCPs) with a central main group element into the porphyrin macrocycle. MGCPs have unique properties, reactivity, and potential applications in catalysis, sensing, biomedicine etc. This comprehensive review article discusses recent advances in the field of main group coordination driven porphyrins and explores some of its potential uses in solar cells, catalysis, antimicrobial, optoelectronic devices, sensing, and catalysis. The addition of main group elements to porphyrin systems has resulted in the production of entirely novel compounds that have intriguing qualities including increased stability and catalytic activity. Significant modifications in these unique compounds features are apparent through the analysis of their structural properties. It encompasses FTIR, proton NMR, electrical and optical characterisation in addition to an electrochemical analysis of those parameters. They serve as significant building blocks for the creation of cutting‐edge materials and technologies in a variety of scientific and technical disciplines because to their special qualities and adaptability. Researchers working in the domains of coordination chemistry, catalysis, and materials science will find this study to be of interest since it offers a thorough examination of current developments in main group coordination driven porphyrins and their prospective applications. Overall, main group porphyrins are used in many different fields, such as sensing, catalysis, and optoelectronic devices.

The Unique Structure–Activity Relationship of Porphyrins and Clay Mineral Systems in Modern Applications: A Comprehensive Review

The Unique Structure–Activity Relationship of Porphyrins and Clay Mineral Systems in Modern Applications: A Comprehensive Review

π‐Conjugated Metal Free Porphyrin as Organic Cathode for Aluminum Batteries

AbstractNowadays, Al (dual) batteries are mainly based on graphite cathode materials. Besides this material, the limited life cycle and the rate performance of other possible cathode materials have hampered the development of practical and sustainable rechargeable aluminium batteries (RABs). Herein, we report an organic A4‐metal‐free porphyrin system bearing diphenylamimo‐phenyl functional units as an Al‐storage cathode material, which is capable of delivering a reversible capacity of 83 mAh g−1 at 1 A g−1 after 200 cycles and displays a good cycling stability. Achieving such high rate performance opens a pathway to developing practical sustainable cathodes for aluminium batteries.

Effect of adenosine monophosphate on visible-light driven nicotinamide mononucleotide reduction in a system of water-soluble zinc porphyrin and colloidal rhodium nanoparticles

Effect of adenosine monophosphate on visible-light driven nicotinamide mononucleotide reduction in a system of water-soluble zinc porphyrin and colloidal rhodium nanoparticles dispersed with polyvinylpyrrolidone was clarified.

Fe-Ni porphyrin/mesoporous titania thin film electrodes: a bioinspired nanoarchitecture for photoelectrocatalysis.

Porphyrin and porphyrinoid derivatives have been extensively studied in the assembly of catalysts and sensors, seeking biomimetic and bioinspired activity. In particular, Fe and Ni porphyrins can be used for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) by immobilization of these molecular catalysts on semiconductor materials. In this study, we designed a hybrid material containing a crystalline mesoporous TiO2 thin film in which the catalytic centres are Ni-porphyrin (NiP), Fe-porphyrin (FeP), and a NiP/FeP bimetallic system to assess whether the coexistence of both metalloporphyrins improves the OER activity. The obtained photoelectrodes were physicochemically and morphologically characterized through high-resolution FE-SEM images, UV-vis and Raman spectroscopies, cyclic voltammetry, and impedance measurements. The results show a differential behavior of the mono- and bimetallic porphyrin systems, where the Fe(iii) centre in FeP may increase the acidity and lower the reduction potential of the Ni2+/3+ couple when co-deposited with NiP leading to an improved photoelectrochemical water-oxidation performance. We have validated the cooperative effect of both metal complexes within this novel system, where the μ-peroxo-bridged interaction between Fe and Ni is integrated into a supramolecular heterometallic structure of porphyrins.

Intramolecular electrostatic effects on reduction of CO2 to CO by iron porphyrin complexes: Insights from DFT calculations

Iron porphyrin (Por) complexes were found to be highly efficient molecular catalysts for electrocatalytic CO2 reduction and the catalytic performance can be modulated by the modification of ligands. Herein, density functional theory calculations were employed to investigate how the presence of second-sphere anionic carboxylate groups influences the CO2-to-CO conversion by Fe porphyrins. The kinetics and thermodynamics of individual chemical steps in the reaction cycle were systematically studied. Computations indicated that the catalytic active species is the ferrous complex with the two extra electrons being stored in the π system of porphyrin and the rate-determining step is the CO2 binding. The synchronization of the Fe-to-CO2 and ligand-to-Fe electron transfers leads to the formation of FeIII(CO22−)(Por•−). The experimentally observed activity trend could be rationalized by the Brønsted-Evans-Polanyi principle. The electrostatic repulsive between the negatively charged hanging group and the CO2 moiety destabilizes the CO2 adduct and thereby raises the binding energy. Then, the two-step protonation occurs easily to give Fe(II)-CO. The further one-electron reduction triggers the dissociation of CO to regenerate of the formal Fe(I) porphyrin catalyst. The insights gained from this study may be helpful in designing efficient electrocatalysts for CO2 reduction.

Dioxygen Activation and Reduction by a Soluble Iron Phthalocyanine.

Iron ions in a square-planar coordination can bind molecules at the vacant axial positions and are able to transform them in stoichiometric and catalytic reactions. Nature takes advantage of these properties by incorporating iron into porphyrin systems, which play a key role not only in the binding and transport of oxygen, but also in catalytic oxidation and reduction reactions involving cytochrome P450. Although these systems have been studied extensively, there are still unresolved questions regarding the interplay between the iron ions and the surrounding ligands. Phthalocyanines (Pc) create a similar environment for metal atoms and FePc is known for a long time. However, without axial ligands FePc aggregates leading to solids of low solubility. In this work we used a known six-coordinate iron phthalocyanine derivative with bulky substituents and removed the stabilizing axial ligands. The resulting paramagnetic, four-coordinate compound does not aggregate and dissolves well so that NMR spectroscopy can be employed for studying the molecular structure and the reactivity. Solvent molecules bind weakly to the iron centers and oxygen is reduced in the presence of H-atom donors. The stoichiometric and catalytic reactivity with oxygen was studied in more detail.

Further Understanding the Roles of Solvent, Brønsted Acids, and Hydrogen Bonding in Iron Porphyrin-Mediated Carbon Dioxide Reduction.

Improving our understanding of how molecules and materials mediate the electrochemical reduction of carbon dioxide (CO2) to upgraded products is of great interest as a means to address climate change. A leading class of molecules that can facilitate the electrochemical conversion of CO2 to carbon monoxide (CO) is iron porphyrins. These molecules can have high rate constants for CO2-to-CO conversion; they are robust, and they rely on abundant and inexpensive synthetic building blocks. Important foundational work has been conducted using chloroiron 5,10,15,20-tetraphenylporphyrin (FeTPPCl) in N,N-dimethylformamide (DMF) solvent. A related and recent report points out that the corresponding perchlorate complex, FeTPPClO4, can have superior function due to its solubility in other organic solvents. However, the importance of hydrogen bonding and solvent effects was not discussed. Herein, we present a detailed kinetic study of the triflate (CF3SO3-) complex of FeTPP in DMF and in MeCN using a range of phenol Brønsted acid additives. We also detected the formation of Fe(III)TPP-phenolate complexes using cyclic voltammetry experiments. Importantly, our new analysis of apparent rate constants with different added phenols allows for a modification to the established mechanistic model for CO2-to-CO conversion. Critically, our improved model accounts for hydrogen bonding and solvent effects by using simple hydrogen bond acidity and basicity descriptors. We use this augmented model to rationalize function in other reported porphyrin systems and to make predictions about operational conditions that can enhance the CO2 reduction chemistry.

A Personal Account on Inorganic Reaction Mechanisms.

The presented Review is focused on the latest research in the field of inorganic chemistry performed by the van Eldik group and his collaborators. The first part of the manuscript concentrates on the interaction of nitric oxide and its derivatives with biologically important compounds. We summarized mechanistic information on the interaction between model porphyrin systems (microperoxidase) and NO as well as the recent studies on the formation of nitrosylcobalamin (CblNO). The following sections cover the characterization of the Ru(II)/Ru(III) mixed-valence ion-pair complexes, including Ru(II)/Ru(III)(edta) complexes. The last part concerns the latest mechanistic information on the DFT techniques applications. Each section presents the most important results with the mechanistic interpretations.

Electronic properties and redox chemistry ofN-confused metalloporphyrins

Here we study the effect of metals on the characteristic Soret band of N-confused porphyrins. We used DFT calculations to study how this low-lying region of the spectrum of the NCP-2H isomer is affected by the introduction of transition metals with various ([Formula: see text], [Formula: see text], [Formula: see text] and [Formula: see text] d-electron configurations. The spin ground state of these complexes is mostly dependent on the number of unpaired electrons, both with and without the presence of an axial ligand. The analysis of the electronic distribution and spin density showed that these unpaired electrons are often harbored by the N-confused porphyrin ring instead of on the metal. Time-dependent DFT results indicated that the aromatic system of porphyrin is disrupted in the N-confused isomer: instead of the typical large Soret band, this now gives rise to two peaks of much lower intensity. Most metallo-porphyrins exhibited similar optical properties, with the HOMO/LUMO orbitals showing a mixed metal/porphyrin character. The only exception was the Rh metalloporphyrin that exhibited a ligand-to-metal charge transfer band with increasing intensity as function of the ligand field. This suggests Rh is the only metal whose orbitals are higher in energy than the ligand’s, indicating that it is the only system where the redox processes occur on the metal.

Influence of local chemical environment and external perturbations of porphyrins on surfaces

Porphyrins and tetrapyrroles play crucial roles in biological processes such as photosynthesis and molecular transport. These nature-based molecules have found application in artificial systems, such as sensing, catalysis, and 2D/3D networks. They are ideal building blocks due to their chemical diversity, stability, and ability to self-assemble on surfaces. Derivatization of the peripheral positions allows for the rational design of magnetic, catalytic, and photochemical properties. Due to this, porphyrins have been used in a variety of natural and artificial systems such as photodynamic therapies and dye-sensitized solar cells. Recently, much work and attention have focused on using specific porphyrin and molecular relatives for molecular electronics due to their robust nature, functionality, and synthesis. The focus of this review is to summarize the mechanisms that affect the internal structure and properties of the molecules and how changes in the local chemical environment alter the electronic properties of the porphyrin. We review the current state of the literature concerning the intermolecular and surface-adsorbate interactions that dictate self-assembly. We will assess the effects that molecule-molecule and molecule-substrate interactions play on the molecule’s properties and the effects that external forces have on the molecular properties. The goal of this review is to dissect the mechanisms responsible for the unique properties that arise from porphyrinic systems adsorbed on surfaces.

Polylactide-Meso-Substituted Arylporphyrin Composites: Structure, Properties and Antibacterial Activity.

The structural features and antibacterial properties of polymer-porphyrin composites were investigated. Meso-substituted arylporphyrin 0.2-0.5 wt.% was immobilized in a polylactide matrix. The immobilization of porphyrin causes a bathochromic shift and splitting of the Soret band. This study of the morphology of the obtained composites demonstrated a uniform distribution of the meso-substituted arylporphyrin in the polylactide matrix. It was determined by the X-ray diffraction analysis that porphyrin does not affect the α-form of polylactide crystalline formations. However, its addition into the polymer somewhat reduces the melting point (by 1-2 °C) and the degree of crystallinity of polylactide (by 3-4%). The elastic characteristics of the resulting systems were determined by the ultrasonic method, and a decrease in the density of the samples with an increase of the arylporphyrin content was shown. According to the results of the biological test, the dark toxicity of the obtained composites against the microorganisms Staphylococcus aureus, Salmonella Typhimurium and Escherichia coli was shown. Immobilizates containing 0.4 and 0.5 wt.% porphyrin showed the best antibacterial effect. The antibacterial activity of the studied composites makes it possible to attribute the polylactide-porphyrin systems to promising materials in the field of medicine and bioengineering.

Facile Synthesis of β-Tetracyano Vanadyl Porphyrin from Its Tetrabromo Analogue and Its Excellent Catalytic Activity for Bromination and Epoxidation Reactions.

Complex 2,3,12,13-tetracyano-5,10,15,20-tetraphenylporphyrinatooxidovanadium(IV) {[VIVOTPP(CN)4], 2} has been prepared by nucleophilic substitution of β-bromo groups of the corresponding 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyrinatooxidovanadium(IV) {[VIVOTPP(Br)4], 1} using CuCN in quinoline. Both complexes show biomimetic catalytic activity similar to enzyme haloperoxidases and efficiently brominate various phenol derivatives in the presence of KBr, H2O2, and HClO4 in the aqueous medium. Between these two complexes, 2 exhibits excellent catalytic activity with high turnover frequency (35.5-43.3 s-1) due to the strong electron-withdrawing nature of the cyano groups attached at β-positions and its moderate nonplanar structure as compared to 1 (TOF = 22.1-27.4 s-1). Notably, this is the highest turnover frequency value observed for any porphyrin system. The selective epoxidation of various terminal alkenes using complex 2 has also been carried out, and the results are good, specifying the importance of electron-withdrawing cyano groups. Catalysts 1 and 2 are recyclable, and the catalytic activity proceeds through the corresponding [VVO(OH)TPP(Br)4] and [VVO(OH)TPP(CN)4] intermediates, respectively.

Dynamic Electron Polarization Lasting More Than 10 μs by Hybridizing Porphyrin and TEMPO with Flexible Linkers.

Dynamic electron polarization (DEP), induced by quenching of photoexcited species by stable radicals, can hyperpolarize electron spins in solution at room temperature. Recently, development of technologies based on electron spin polarization such as dynamic nuclear polarization (DNP) has been progressing, where it is important to design molecules that achieve long-lasting DEP in addition to high DEP. Hybridization by linking dyes and radicals is a promising approach for efficient DEP, but strong interactions between neighboring dyes and radicals often result in the rapid decay of DEP. In this study, we introduce a flexible linker into the hybrid system of porphyrin and TEMPO to achieve both efficient DEP and long-lasting DEP. The structural flexibility of the linker switches the interaction between the radical and the triplet, which promotes the DEP process by bringing the radical and the triplet into close proximity, while avoiding abrupt relaxation due to strong interactions. As a result, the new hybridized system exhibits a larger DEP than the unlinked system, while at the same time achieving a DEP lasting more than 10 μs.

An exchange coupled meso-meso linked vanadyl porphyrin dimer for quantum information processing.

We report here the synthesis of a new meso-meso (m-m) singly linked vanadyl-porphyrin dimer that crystallizes in two different pseudo-polymorphs. The single crystal continuous-wave electron paramagnetic resonance investigation evidences a small but crucial isotropic exchange interaction, J, between the two tilted, and thus distinguishable, spin centers of the order of 10-2 cm-1. The experimental and DFT studies evidence a correlation between J values and porphyrin plane tilting angle and distortion. Pulsed EPR analysis shows that the two vanadyl dimers maintain the coherence time of the monomer. With the obtained spin Hamiltonian parameters, we identify suitable transitions that could be used as computational basis states. Our results, coupled with the evaporability of porphyrin systems, establish this class of dimers as extremely promising for quantum information processing applications.

Investigation of organic solar cells with highly porous 3D-titania aerogel sensitization, optical and electrochemical properties of metal-free porphyrin dyes with 3-methyl-4-hydroxy phenyl functionality

An anchoring group is necessary for linking dye and photoanode as an array. The inter-electron transfer between the layers produces the photoelectron when it is exciting. The introduction of a novel 3-methyl-4-hydroxy phenyl anchoring group to the porphyrin periphery and its potential use in organic solar cell (OSC) applications were addressed. The bare dyes are soaked with a titania aerogel photoanode. FT-IR, UV–visible, and CV spectral analyses further study the electron transfer mechanism at the TA/dye interfaces. The 3-methyl-4-hydroxy phenyl anchor's two attachment points to the titania aerogel (TA) surface were validated by FT-IR at 1630 and 1400 cm−1. The spectrum broadening and band shift after TA adsorption show the dyes' electronic coupling and aggregation features. In order to provide more insights into the kinetics of electron transfer, the exact HOMO and LUMO energy levels are estimated, and the energy level diagram compares the conductance of TA and electrolyte potential. The 3-methyl-4-hydroxy phenyl anchor was used to demonstrate the ability of the dye/TA photoanode to generate an electrical current as an OSC device. The effects of the subsequent change in photocurrent on the number of anchoring groups in the metal-free porphyrin system are studied.

Theoretical analysis of expanded porphyrins: Aromaticity, stability, and optoelectronic properties

Expanded porphyrin systems are capable of binding a variety of substrates due to their increased cavity size and aromatic nature, holding important applications as magnetic resonance imaging contrast agents and as sensitizers for photodynamic therapy. It is there of fundamental interest to know the photoelectrical properties of expanded porphyrins using quantum chemistry calculations. In this work, we theoretically designed and screened a series of expanded porphyrins by incorporating terthiophene (TTH) and dithienothiophene (DTT) moieties. Our calculations showed that all the designed molecules exhibit excellent optoelectronic performance than the reference molecule. It is suggested that the porphyrin molecule with TTH moiety has better stability than the one with DTT moiety. Finally, we demonstrated that molecule 2 features with TTH moiety and the inverted selenophene ring outperform other molecules because it exhibits increased HOMO-LUMO gap, planar geometry, and strengthened aromaticity. We expect that this work can provide theoretical guidelines for the design of novel porphyrin materials.

Even Odd Oscillation in Tunnelling Magneto Resistance of Transition metal doped Metallo Porphyrin systems

Herein we report variation in Tunnelling magneto resistance (TMR) of TM-porphyrin against increase in d electrons from n=1 to 8; as the transition metal changes across the periodic table from Sc to Ni. We observed that highest value of TMR is observed for d5 system the TMR becomes gigantic (1022) at the equilibrium and on either side of it we need to apply certain amount of energy to reach appreciable TMR. An even-odd oscillation of TMR is observed against the number of electrons in d orbital. We also observed that with even number of d electrons TMR values is on lower side and in many cases below the accepted range (150%) of an efficient TMR device. In fact, to achieve an acceptable range we need to apply relatively larger energy (as large as 0.7 eV for Ni) probably due to preference of low spin states in presence of even number of electrons in an atom. Observed feature has been explained using molecular orbital obtained in each case.