Search Results (17)

Rhodium–porphyrin complexes are characterised by their ability to activate C-H and C-C bonds and, therefore, find applications in synthesis and catalysis. Axial rhodoporphyrin ligands are susceptible to photodissociation under the influence of light. DFT and TDDFT calculations were performed to investigate the mechanism of photodissociation of the methyl ligand from the methylrhodium(III)–porphyrin complex (MeRhPor). Various photolysis pathways of the rhodium–methyl bond were investigated, including photolysis from states in the Q and Soret bands. Photolysis from triplet states was also considered. Based on the calculations, the most probable mechanism for photodissociation of the methyl ligand was proposed. The methyl-rhodium binding energy in the methylrhodium(III)–porphyrin complex and the energy of formation of the rhodium–porphyrin radical dimer formed by methyl dissociation were also calculated. Full article

Iron porphyrins are known to provide CH₄ as an eight-electron reduction product of CO₂ in a photochemical reaction. However, there are still some aspects of the reaction mechanism that remain unclear. In this study, we synthesized iron porphyrin dimers and carried out the photochemical CO₂ reduction reactions in N,N-dimethylacetamide (DMA) containing a photosensitizer in the presence of 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) as an electron donor. We found that, despite a low catalytic turnover number, CH₄ was produced only when these porphyrins were facing each other. The close proximity of the cyclic dimers, distinguishing them from a linear Fe porphyrin dimer and monomers, induced multi-electron CO₂ reduction, emphasizing the unique role of their structural arrangement in CH₄ formation. Full article

The syntheses of a series of copper(II) porphyrins and their dimers linked by palladium(II) or platinum(II) are reported. Their electronic properties and their magnetic properties were studied. In particular, the effect of the linking unit on these properties was evaluated. It was discovered that three factors influence the electronic and magnetic interactions between the two metalloporphyrins: the nature of the linking metal ion, the nature of the external coordination site of the porphyrin, and also the nature of the metal ion present in the central core of the aromatic macrocycle. Full article

In this work, a number of new porphyrin dimers coupled with spacers based on α,α’-dibromo-o-xylene were synthesized and characterized by ¹H, ¹³C NMR, ¹H-¹H COSY NMR, UV-vis-spectroscopy, and MALDI-TOF mass spectrometry. The initial A3B-type hydroxy-substituted porphyrins form dimer structures with high yields of 80–85%, while the use of amino-substituted porphyrins as starting compounds leads to the heterocyclization and formation of N-heterocycle fused porphyrins. For porphyrin dimers, photophysical properties and quantum yields of singlet oxygen were investigated. The peripheral alkoxy-substituents increase fluorescence quantum yield in comparison with the unsubstituted compounds. Also, it was found that dimers are characterized by lower singlet oxygen quantum yields compared to the corresponding monomers. Model aggregation experiments in micellar systems demonstrate stabilization of the photoactive monomolecular form of all the porphyrins, using nonionic surfactant Triton X-100. Cytotoxicity of received dimers shows high inhibition against HEK293T cells in the absence of light. Full article

A simple and efficient protocol is utilized for the transformation studies of a thiophene analog of E-resveratrol by photocatalytic oxygenation using an anionic and a cationic free-base porphyrin, as well as their manganese(III) complexes. The starting substrate was chosen as a representative of heterostilbenes with proven good antioxidant activity. The experiments were carried out in two photoreactor types (batch and microflow reactor) to investigate the impact of the reactor type and design on conversion and photoproduct composition. NMR spectroscopy and UHPLC/MS analyses were applied for the identification and quantification of four photoproducts (Z-1, 2, 3, and 4), results of isomerization, dimerization, cyclization, and oxygenation. Different yields of photoproducts were obtained in a batch reactor and microflow reactor. In the experiments performed in a microflow reactor, Z-1 was most dominant because it was constantly removed from the reaction mixture. Therefore, the formation of other products (2, 3, 4, and undefined) whose precursor is Z-1 was avoided. This was not the case in the experiments performed in a batch reactor. Additionally, all the reactions tested were significantly accelerated in a microflow reactor, making it the preferred reactor type and design for the photocatalytic transformation of resveratrol derivative. Full article

A cytochrome c₅₅₂ mutant from Thermus thermophilus HB8 (rC₅₅₂ C14A) was reported, where the polypeptide with replaced Cys14 by alanine, overexpressed in the cytosol of E. coli. The apo-form of the C14A mutant (apo-C14A) without the original prosthetic group was obtained by simple chemical treatments that retained compact conformation amenable to reconstitution with heme b and zinc(II)-protoporphyrin(IX), gradually followed by spontaneous formation of a covalent bond between the polypeptide and porphyrin ring in the reconstituted apo-C14A. Further analysis suggested that the residual Cys11 and vinyl group of the porphyrin ring linked through the thiol-ene reaction promoted by light under ambient conditions. In this study, we describe the kinetic improvement of the covalent bond formation in accordance with the mechanism of the photoinduced thiol-ene reaction, which involves a thiyl radical as a reaction intermediate. Adding a radical generator to the reconstituted C14A mutant with either heme-b or zinc(II) porphyrin accelerated the bond-forming reaction, which supported the involvement of a radical species in the reaction. Partial observation of the reconstituted C14A in a dimer form and detection of sulfuryl radical by EPR spectroscopy indicated a thiyl radical on Cys11, a unique cysteinyl residue in rC₅₅₂ C14A. The covalent bond forming mediated by the radical generator was also adaptable to the reconstituted apo-C14A with manganese(II)-protoporphyrin(IX), which also exhibits light-mediated covalent linkage formation. Therefore, the radical generator extends the versatility of producing c-type-like cytochrome starting from a metallo-protoporphyrin(IX) and the apo-C14A instantaneously. Full article

In the present work, the first data on the catalytic activity of d-metal complexes of petroleum porphyrins obtained via two-stage re-metallization (acid demetallization with subsequent metalation) of high-purity petroleum vanadyl porphyrins are presented. During acid demetallization of petroleum vanadyl porphyrins, the highest yield (49%) and spectral purity of free petroporphyrin bases were achieved with concentrated sulfuric acid and a diluted solution of vanadyl porphyrins in chloroform. In the series of divalent cations of Mn, Fe, Co, Ni, Cu, and Zn, only the last four metals are complexed with demetallated petroporphyrins without significant changes in their component composition, whereas the interaction with Mn and Fe cations causes an evident structural transformation or even full degradation of petroporphyrin macrocycles, respectively. The composition and spectral purity of petroleum porphyrin-containing reactants and products were analyzed by FT-IR, UV-Vis, NMR, and MALDI-TOF mass spectroscopic methods. The obtained petroporphyrin-based d-metal complexes were assayed by the reaction of 2-mercaptoethanol oxidative dimerization, in which the copper porphyrins exhibited the highest catalytic activity. Full article

The hierarchical self-assembling kinetics of the porphyrin 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H₂TPPS₄⁴⁻) into J-aggregates at high ionic strength under acidic conditions and eventually in the presence of an added chiral templating agent (tartrate) were investigated through UV/Vis spectroscopy, resonance light scattering, and circular dichroism (CD). The effect of changing the mixing order of the various components in the solution on the kinetic parameters and the expression of chirality on the final J-aggregates was evaluated. In this latter case, only when the chiral tartrate anion is premixed with the porphyrin, the resulting nano-architectures exhibit CD spectra that reflect the handedness of the chiral inducer. We discuss a general mechanistic scheme, with the involvement of ion pairs or dimers that offer an alternative pathway to the aggregation process. Full article

Blood-pool agents (BPAs) are MRI contrast agents (CAs) characterized by their long circulation in the vascular system to provide an extended time window for high-resolution MR angiography (MRA). Prolonged vascular retention, however, impedes the excretion of BPAs. Therefore, chemical strategy to regulate the balance between retention and clearance is important to reach optimal pharmacokinetics. We recently developed MnP2, the first Mn(III)-porphyrin (MnP) based BPA. MnP2 shows high T₁ relaxivity (r₁) and high affinity to human serum albumin (HSA) that leads to up to 48-h vascular retention in rats. However, upon albumin binding, the r₁ is decreased. To modulate vascular retention time and plasma r₁, a regioisomer of MnP2, m-MnP2, was synthesized. The free m-MnP2 exhibits lower r₁ than that of MnP2 at magnetic fields above 2 MHz, which agrees with their relative hydrodynamic sizes. The HSA binding of m-MnP2 was evaluated using UV-Vis spectroscopy and found to have tuned-down affinity in comparison with MnP2. Upon HSA binding, the protein complex of m-MnP2 exhibits an r₁ of 11.8 mM⁻¹ s⁻¹ at 3 T, which is higher than that of MnP2 bound to HSA. Taken together, this demonstrated the role of molecular geometry in optimizing the pharmacokinetics of albumin-targeting BPAs. Full article

Owing to the attractive potential applications of porphyrin assemblies in photocatalysis, sensors, and material science, studies presently concerning porphyrin aggregation are widely diffused. π–π stacking, H-bonding, metal coordination, hydrophobic effect, and electrostatic forces usually drive porphyrin interaction in solution. However, theoretical studies of such phenomena are still limited. Therefore, a computational examination of the different porphyrin aggregation approaches is proposed here, taking into account amphiphilic [5-{4-(3-trimethylammonium)propyloxyphenyl}-10,15,20-triphenylporphyrin] chloride, whose aggregation behavior has been previously experimentally investigated. Different functionals have been adopted to investigate the porphyrin dimeric species, considering long-range interactions. Geometry optimization has been performed, showing that for the compound under analysis, H-type and cation–π dimers are the most favored structures that likely co-exist in aqueous solution. Of note, frontier orbital delocalization showed an interesting interaction between the porphyrin units in the dimer at the supramolecular level. Full article

The synthesis and surface self-assembly behavior of two types of metal-porphyrin dimers is described. The first dimer type consists of two porphyrins linked via a rigid conjugated spacer, and the second type has an alkyne linker, which allows rotation of the porphyrin moieties with respect to each other. The conjugated dimers were equipped with two copper or two manganese centers, while the flexible dimers allowed a modular built-up that also made the incorporation of two different metal centers possible. The self-assembly of the new porphyrin dimers at a solid–liquid interface was investigated at the single-molecule scale using scanning tunneling microscopy (STM). All dimers formed monolayers, of which the stability and the internal degree of ordering of the molecules depended on the metal centers in the porphyrins. While in all monolayers the dimers were oriented coplanar with respect to the underlying surface (‘face-on’), the flexible dimer containing a manganese and a copper center could be induced, via the application of a voltage pulse in the STM setup, to self-assemble into monolayers in which the porphyrin dimers adopted a non-common perpendicular (‘edge-on’) geometry with respect to the surface. Full article

Since water-soluble porphyrin complexes of lanthanides(III) have proved to be promising for medical applications (e.g., luminescence imaging, photodynamic therapy, and theranostics), the investigation of the formation, photophysical, and photochemical properties of such coordination compounds provides useful pieces of information for their potential usage. Steady-state and time-resolved fluorometry, UV–Vis absorption spectroscopy, and continuous-wave photolysis were utilized for this purpose. 5,10,15,20-Tetrakis(4-sulfonatophenyl)porphyrin formed mono- and bisporphyrin complexes with samarium(III), europium(III), and gadolinium(III) as representatives in the middle of the lanthanide series. The special photoinduced behavior of these compounds was mostly determined by the position of the metal center, which was located out of the ligand plane, thus distorting it. Besides, the photochemical and, especially, photophysical features of the corresponding mono- and bisporphyrin complexes were similar because, in the latter species, two monoporphyrins were connected by a weak metal bridge between the peripheral sulfonato substituents (tail-to-tail dimerization). The formation of these coordination compounds and the transformation reactions between the mono- and bisporphyrins were rather slow in the dark at room temperature. These processes were accelerated by visible irradiation. However, dissociation and, especially, redox degradation were the main photoreactions in these systems, although with low quantum yields. Additionally, depending on the excitation wavelength, new types of photoproducts were also detected. Full article

Tetrakis (4-carboxyphenyl) porphyrin (TCPP) and polyelectrolyte poly(N-methyl-2-vinylpyridinium iodide)-b-poly(ethylene oxide) (PMVP₄₁-b-PEO₂₀₅) can self-aggregate into polyion complex (PIC) micelles in alkaline aqueous solution. UV-vis spectroscopy, fluorescence spectroscopy, transmission electron microscope, and dynamic light scattering were carried out to study PIC micelles. Density functional theory (DFT) calculation method was applied to study the interaction of TCPP and PMVP₄₁-b-PEO₂₀₅. We found that the H-aggregates and J-dimers of anionic TCPP transformed in PIC micelles. H-aggregates of TCPP formed at the charge ratio of TCPP/PMVP₄₁-b-PEO₂₀₅ 1:2 and J-dimer species at the charge ratio above 1:4, respectively. It is worth noting that the transformation from H-aggregates to J-dimer species of TCPP occurred just by adjusting the ratio of polymer and TCPP rather than by changing other factors such as pH, temperature, and ions. Full article

Azobenzenes are versatile compounds with a range of applications, including dyes and pigments, food additives, indicators, radical reaction initiators, molecular switches, etc. In this context, we report a general method for synthesizing o-aminoazobenzenes using the commercially available cobalt(II) tetraphenyl porphyrin [Co^II(TPP)]. The net reaction is a formal dimerization of two phenyl azides with concomitant loss of two molecules of dinitrogen. The most commonly used methodology to synthesize azobenzenes is based on the initial diazotization of an aromatic primary amine at low temperatures, which then reacts with an electron rich aromatic nucleophile. As such, this limits the synthesis of azobenzenes with an amine functionality. In contrast, the method we report here relies heavily on the o-amine moiety and retains it in the product. The reaction is metal catalyzed and proceeds through a porphyrin Co(III)-nitrene radical intermediate, which is known to form on activation of organic azides at the cobalt center. The synthesized o-aminoazobenzenes are bathochromatically shifted, as compared to azobenzenes without amine substituents. Based on the crystal structure of one of the products, strong H-bonding between the N-atom of the azo functionality and the H of the NH₂ substituent is shown to stabilize the trans isomeric form of the product. The NH₂ substituents offers possibilities for further functionalization of the synthesized azo compounds. Full article

The successful preparation of a novel dimer complex formed between 5,10,15,20-tetrakis(3,4-dimethoxyphenyl)-porphyrin Fe(III) chloride and (5,10,15,20-tetraphenylporphinato) dichlorophosphorus(V) chloride using the well-known reactivity of the P–X bond is reported. The obtained complex was characterized by UV-vis, Fourier transform infrared spectroscopy (FT-IR), fluorescence, ¹H-NMR, ¹³C-NMR, and ³¹P-NMR spectroscopic techniques and also by additional Heteronuclear Single Quantum Coherence (HSQC) and Heteronuclear Multiple Bond Correlation (HMBC) experiments in order to correctly assign the NMR signals. Scanning electron microscopy (SEM) and EDX quantifications completed the characterizations. This novel porphyrin dimer complex demonstrated fluorescence sensing of H₂O₂ in water for low oxygen concentrations in the range of 40–90 µM proving medical relevance for early diagnosis of diseases such as Alzheimer’s, Parkinson’s, Huntington’s, and even cancer because higher concentrations of H₂O₂ than 50 μM are consideredcytotoxic for life. Due to its optical properties, this novel metalloporphyrin–porphyrin based complex is expected to show PDT and bactericidal activity under visible-light irradiation. Full article