Porphyrin Molecules Research Articles

Influence of Cationic meso-Substituted Porphyrins on the Antimicrobial Photodynamic Efficacy and Cell Membrane Interaction in Escherichia coli.

Photodynamic inactivation (PDI) is a non-antibiotic option for the treatment of infectious diseases. Although Gram-positive bacteria have been shown to be highly susceptible to PDI, the inactivation of Gram-negative bacteria has been more challenging due to the impermeability properties of the outer membrane. In the present study, a series of photosensitizers which contain one to four positive charges (1–4) were used to evaluate the charge influence on the PDI of a Gram-negative bacteria, Escherichia coli (E. coli), and their interaction with the cell membrane. The dose-response PDI results confirm the relevance of the number of positive charges on the porphyrin molecule in the PDI of E. coli. The difference between the Hill coefficients of cationic porphyrins with 1–3 positive charges and the tetra-cationic porphyrin (4) revealed potential variations in their mechanism of inactivation. Fluorescent live-cell microscopy studies showed that cationic porphyrins with 1–3 positive charges bind to the cell membrane of E. coli, but are not internalized. On the contrary, the tetra-cationic porphyrin (4) permeates through the membrane of the cells. The contrast in the interaction of cationic porphyrins with E. coli confirmed that they followed different mechanisms of inactivation. This work helps to have a better understanding of the structure-activity relationship in the efficiency of the PDI process of cationic porphyrins against Gram-negative bacteria.

Exclusive occurrence of photoinduced energy transfer and switching of its direction by rectangular π-extension of nanographenes.

As structure defined cutouts of the graphene lattice, nanographene molecules have gained plenty of attention because of their high potential for versatile applications in organic electronics and energy conversion devices and as ideal model systems for the better understanding of intrinsic structure-property correlations of graphenes. In this study, well-defined nanographenes with sp2 carbon networks of different sizes, hexa-peri-hexabenzocoronene (HBC) and its rectangularly π-extended version, a short graphene nanoribbon (GNR), have been covalently functionalized with photoactive porphyrin molecules. On the basis of their spectroscopic studies, the photodynamics of the porphyrin-linked nanographenes was found to be influenced substantially by the size of the nanographenes. Photoexcitation of the porphyrin-HBC linked system led to exclusive energy transfer (EnT) from the first singlet excited state (S1) of the nanographene to the porphyrin, whereas opposite selective EnT occurred from the first and second singlet excited states (S1 and S2) of the porphyrin to the nanographene in the porphyrin-GNR linked system. In particular, ultrafast efficient EnTs from both the S2 and S1 states of the porphyrin to GNR mimic the corresponding ultrafast EnTs from the S2 and S1 states of carotenoids to chlorophylls in light-harvesting systems of natural photosynthesis. Such unique photophysical properties will be useful for the rational design of carbon-based photofunctional nanomaterials for optoelectronics and solar energy conversion devices.

Highly Active Catalysis of Cobalt Tetrakis(pentafluorophenyl)porphyrin Promoted by Chitosan for Cyclohexane Oxidation in Response-Surface-Methodology-Optimized Reaction Conditions.

We aimed at elevating catalytic performances of cobalt tetrakis(pentafluorophenyl)porphyrin (Co TPFPP) through axial coordination, nanocavities, and covalently grafting action. The Co TPFPP was immobilized onto nanoporous and nonporous chitosan, forming Co TPFPP/np‐ and nonp‐CTS catalysts, respectively. The catalysts were characterized by various spectroscopic techniques. The catalytic performances of these catalysts for cyclohexane oxidation under response‐surface‐methodology‐optimized oxidation reaction conditions were estimated and compared. Co TPFPP/np‐CTS was an excellent catalyst at aspect of catalytic activity, exhibiting the considerable potential reusability, 24.2 mol % yields (KA oil : cyclohexanone and cyclohexanol) in average, and total turnover frequencies (TOFs) of 3.25×106 h−1. This is attributed to the structural characteristics of the Co TPFPP/np‐CTS catalyst: the cobalt porphyrin molecules could be highly scattered on CTS, forming the independent active sites, and were not leached. The axial coordination exerted the most important effect on the catalytic activity, and the covalent grafting action had a decisive effect on the increase of the total TOFs and on the reusability of the catalyst.

Spectroscopic study of the loading of cationic porphyrins by carbon nanohorns as high capacity carriers of photoactive molecules to cells

Spherical carbon nanohorns have great potential as drug delivery agents. Here a detailed study of the loading of porphyrin molecules is reported and the influence on their stability described. An optimally loaded sample is shown to cause photoactivated cell death.

Charge transport pathways in metal porphyrin as interplay between long and short range scattering processes

We have investigated the ballistic transport for Mn, Fe–porphyrin molecules in contact with Au(111) electrodes by using density functional theory. We show that the information resulted from the projected density of electronic states does not provide a complete picture of the transport mechanism. Instead, we propose a methodology based on the concept of the orbital projected transmissions for selected groups of atoms. We have found that the transmission channels for occupied states can be assigned to short range scattering processes at gold-molecule interface, while for the states above Fermi level the transmission takes place via long range scattering processes. The interplay between these two conduction mechanisms is responsible for the transport path in metal–porphyrin; our model is in qualitative agreement with the existing experimental data on transport pathway on single porphyrin molecules.

Study of Substituent Effect on Properties of Platinum(II) Porphyrin Semiconductor Using Density Functional Theory

Study of substituent effect on properties of platinum(II) porphyrin had been performed using DFT method. The aim of the study is to investigate the effect of substituent group on the electronic and optical properties of the platinum(II) porphyrin. Geometry optimization was conducted using DFT/B3LYP/LANL2DZ to obtain molecular structure, electronic structure and energy profile. Band gap energy (Eg), the density of states (DOS), and UV-visible spectra are the semiconductor parameters to study. Computational results show that platinum(II) porphyrin and substituted platinum(II) porphyrin have properties of semiconductor based on Eg value, DOS, and UV-visible spectra. The results show that Mulliken partial charges of electron withdrawing substituents are higher than the electron donating substituents (CH3, OH, and NH2). Eg values of the complexes with respect to the substituents follow this order: NH2 < OH < NO2 < COOH < I < CH3 < Br < F < H, for DOSHOMO values, the order is CH3 < NO2 < I < OH < F < NH2 < COOH < Br < H and the maximum wavelength (λmax) for UV-visible adsorption spectra follows this order: NH2 > OH > COOH > NO2 > I > Br > CH3 > F > H. Molecules with smaller Eg and DOSHOMO values and higher λmax are considered as the most appropriate semiconductor materials. Our results show that Pt(II)P-NH2 has the smallest Eg and the highest λmax among other substituted platinum(II) porphyrin molecules. Therefore, Pt(II)P-NH2 are the most suitable semiconductor material based on the aforementioned criteria.

Design of Single-Molecule Multiferroics for Efficient Ultrahigh-Density Nonvolatile Memories.

It is known that an isolated single‐molecule magnet tends to become super‐paramagnetic even at an ultralow temperature of a few Kelvin due to the low spin switching barrier. Herein, single‐molecule ferroelectrics/multiferroics is proposed, as the ultimate size limit of memory, such that every molecule can store 1 bit data. The primary strategy is to identify polar molecules that possess bistable states, moderate switching barriers, and polarizations fixed along the vertical direction for high‐density perpendicular recording. First‐principles computation shows that several selected magnetic metal porphyrin molecules possess buckled structures with switchable vertical polarizations that are robust at ambient conditions. When intercalated within a bilayer of 2D materials such as bilayer MoS2 or CrI3, the magnetization can alter the spin distribution or can be even switched by 180° upon ferroelectric switching, rendering efficient electric writing and magnetic reading. It is found that the upper limit of areal storage density can be enhanced by four orders of magnitude, from the previous super‐paramagnetic limit of ≈40 to ≈106 GB in.−2, on the basis of the design of cross‐point multiferroic tunneling junction array and multiferroic hard drive.

Single photon nonlinear absorption spectroscopy of cascade energy level systems

Theoretically discussed the third order nonlinear optical properties and absorption cross-sections in two and three level cascade systems by considering single photon resonant absorption at 671 nm of CW laser. The results indicate that while two level system producing Single Saturable Absorption (SSA), it is possible to obtain Double Saturable Absorption (DSA) and Reverse Saturable Absorption (RSA) with long range and modulation depth by tuning the spectroscopic parameters like absorption cross-section and lifetime of participating levels in three level system. Analytical expressions have been given for nonlinear coefficients of the electromagnetic wave equation by considering the propagation in two and three level cascade media. The gradient refractive index formed in single and double beam interaction with the material was discussed. The origin of large phase distortion in the z-scan closed aperture and formation of nonlinear grating in the degenerative four wave mixing are discussed. To emphasize the theoretical results, the discussion has been extended to explain the third order nonlinear experimental results of porphyrin molecules in the degenerative four wave mixing and z-scan techniques.

High-Performance Near-Infrared Absorbing n-Type Porphyrin Acceptor for Organic Solar Cells.

While the outstanding charge transport and sunlight-harvesting properties of porphyrin molecules are highly attractive as active materials for organic photovoltaic (OPV) devices, the development of n-type porphyrin-based electron acceptors has been challenging. In this work, we developed a high-performance porphyrin-based electron acceptor for OPVs by substitution of four naphthalene diimide (NDI) units at the perimeter of a Zn-porphyrin (PZn) core using ethyne linkage. Effective π-conjugation between four NDI wings and the PZn core significantly broadened Q-band absorption to the near infrared region, thereby achieving the narrow band gap of 1.33 eV. Employing a windmill-structured tetra-NDI substituted PZn-based acceptor ( PZn-TNDI) and mid-band gap polymer donor (PTB7-Th), the bulk heterojunction OPV devices achieved a power conversion efficiency (PCE) of 8.15% with an energy loss of 0.61 eV. The PCE of our PZn-TNDI-based device was the highest among the reported OPVs using porphyrin-based acceptors. Notably, the amorphous characteristic of PZn-TNDI enabled optimization of the device performance without using any additive, which should make industrial fabrication simpler and cheaper.

Emerging Applications of Porphyrins and Metalloporphyrins in Biomedicine and Diagnostic Magnetic Resonance Imaging.

In recent years, scientific advancements have constantly increased at a significant rate in the field of biomedical science. Keeping this in view, the application of porphyrins and metalloporphyrins in the field of biomedical science is gaining substantial importance. Porphyrins are the most widely studied tetrapyrrole-based compounds because of their important roles in vital biological processes. The cavity of porphyrins containing four pyrrolic nitrogens is well suited for the binding majority of metal ions to form metalloporphyrins. Porphyrins and metalloporphyrins possess peculiar photochemical, photophysical, and photoredox properties which are tunable through structural modifications. Their beneficial photophysical properties, such as the long wavelength of emission and absorption, high singlet oxygen quantum yield, and low in vivo toxicity, have drawn scientists’ interest to discover new dimensions in the biomedical field. Applications of porphyrins and metalloporphyrins have been pursued in the perspective of contrast agents for magnetic resonance imaging (MRI), photodynamic therapy (PDT) of cancer, bio-imaging, and other biomedical applications. This review discusses photophysics and the photochemistry of porphyrins and their metal complexes. Secondly, it explains the current developments and mode of action for contrast agents for MRI. Moreover, the application of porphyrin and metalloporphyrin-based molecules as a photosensitizer in PDT of cancer, the mechanism of the generation of reactive oxygen species (ROS), factors that determine the efficiency of PDT, and the developments to improve this technology are delineated. The last part explores the most recent research and developments on metalloporphyrin-based materials in bio-imaging, drug delivery, and the determination of ferrochelatase in bone marrow indicating their prospective clinical applications.

Magnetic Targeting of Nanotheranostics Enhances Cerenkov Radiation-Induced Photodynamic Therapy.

The interaction between radionuclides and nanomaterials could generate Cerenkov radiation (CR) for CR-induced photodynamic therapy (PDT) without requirement of external light excitation. However, the relatively weak CR interaction leaves clinicians uncertain about the benefits of this new type of PDT. Therefore, a novel strategy to amplify the therapeutic effect of CR-induced PDT is imminently required to overcome the disadvantages of traditional nanoparticulate PDT such as tissue penetration limitation, external light dependence, and low tumor accumulation of photosensitizers. Herein, magnetic nanoparticles (MNPs) with 89Zr radiolabeling and porphyrin molecules (TCPP) surface modification (i.e., 89Zr-MNP/TCPP) were synthesized forCR-induced PDT with magnetic targeting tumor delivery. As a novel strategy to break the depth and light dependence of traditionalPDT, these 89Zr-MNP/TCPP exhibited high tumor accumulation under the presence of anexternal magnetic field, contributing to excellent tumor photodynamic therapeutic effect together with fluorescence, Cerenkov luminescence (CL), and Cerenkov resonance energy transfer (CRET) multimodal imaging to monitor the therapeutic process. The present study provides a major step forward in photodynamic therapy by developing an advanced phototherapy tool of magnetism-enhanced CR-induced PDT for effective targeting and treatment of tumors.

Intercalating Single-Atom Metal Centers into an Organic Monolayer with a Full-Sample Coverage.

Thiolate self-assembled monolayers (SAMs) have been widely used as a straightforward method to functionalize the surface of a common substrate with selective organic functional groups. Here we describe a process that further introduces isolated metal centers into an organic SAM using solutions of metallic porphyrin so that different organic groups and metal single-atoms can be simultaneously exposed on top of the surface. The entire process employs only common laboratory equipment and mild-temperature (<100 °C) incubation to create a full-sample (>cm2) SAM coverage. Each step in this process is closely monitored and discussed using nm-scale scanning tunneling microscopy (STM) images. This work can be straightforwardly adopted by research groups interested in such a diversely customizable surface but without access to a vacuum-based deposition technology. The porphyrin molecules are shown to intercalate among closely packed thiolate SAM domains, and STM characterization shows that the entire mixed monolayer is stable in an ambient condition. This process also does not involve any tip-assisted desorption or lithography procedure and can thus be applied toward substrates of other shapes beyond a flat surface.

Porphyrin–High-Density Lipoprotein: A Novel Photosensitizing Nanoparticle for Lung Cancer Therapy

We have developed ultrasmall porphyrin-high-density lipoprotein (HDL) nanoparticles (<20 nm), called "porphyrinHDL," that have a high density of porphyrin molecules and dissociate rapidly upon tumor cell accumulation to become fluorescent and photoactive. This is introduced as a novel activatable photosensitizer for image-guided photodynamic therapy (PDT). Here, we report the studies of these nanoparticles targeted to scavenger receptor class B type I (SR-BI) expressed on lung cancer cells as a first step toward development of a minimally invasive treatment for peripheral lung cancer and metastatic lymph nodes of advanced lung cancer. The invitro uptake of porphyrinHDL and the corresponding PDT efficacy were evaluated in both SR-BI-positive and SR-BI-negative lung cancer cell lines. A clinically relevant orthotopic lung cancer model in mice was used to examine fluorescence activation and quantification of uptake in tumor. In addition, we investigated the effect of porphyrinHDL-mediated PDT. PorphyrinHDL promoted proper intracellular uptake in the H460 human lung cancer cell line. When irradiated with a 671-nm PDT laser, porphyrinHDL produced significant therapeutic effectiveness invitro. After systemic administration in mice with orthotopic lung cancer xenografts, porphyrinHDL demonstrated selective accumulation and photoactivation in tumor with significantly enhanced disease-to-normal tissue contrast. Moreover, porphyrinHDL-PDT significantly induced cell apoptosis in lung tumors (73.2%) without toxicity in normal tissues or damage to adjacent critical structures. SR-BI-targeted porphyrinHDL-mediated PDT of lung cancer is selective and effective invitro and invivo. These initial proof-of-principle studies suggest the potential of a "smart" PDT approach for highly selective tumor ablation.

Hierarchical Assembly of l-Phenylalanine-Terminated Bolaamphiphile with Porphyrin Show Tunable Nanostructures and Photocatalytic Properties.

Demands related to clean energy and environmental protection promote the development of novel supramolecular assemblies for photocatalysis. Because of the distinctive aggregation behaviors, bolaamphiphiles with two hydrophilic end groups could be theoretically the right candidates for the fabrication of high-performance photocatalysis. However, photocatalytic applications based on bolaamphiphilic assemblies were still rarely investigated. Especially, the relationship between diverse assembled nanostructures and the properties for different applications is urgently needed to be studied. Herein, we demonstrate that using the hierarchical assembly of bolaamphiphiles could correctly induce the porphyrin supramolecular architectures with much better photocatalytic performances than the aggregations containing 450 times of the porphyrin molecules, even though both molecular structures as well as the J-aggregations of porphyrin building blocks are same in two different systems. Thus, the co-assembly of l-phenylalanine terminated bolaamphiphile (Bola-F) and the porphyrin containing four hydroxyl groups (tetrakis-5,10,15,20-(4-hydroxyphenyl)porphyrin) can form microtube in methanol and forms fibers/spheres in methanol/water mixture. For catalyzing the photodegradation of rhodamine B, the small amount of J-aggregated porphyrin within Bola-F microtubes show much better photocatalytic performance comparing with that of huge porphyrin J-aggregations in fibers/spheres. The supramolecular assemblies as well as the photocatalysis were thoroughly characterized by different spectroscopies and electron microscopy. It is demonstrated that the co-assembly with bolaamphiphiles could inhibit the energy transfer of porphyrin aggregation and subsequently benefit the electron transfer and corresponding photocatalysis under photo-irradiation. This work is not only useful for further understanding the hierarchically supramolecular assembly but also provides a new strategy for making novel functional supramolecular architectures based on the assembly of bolaamphiphiles and porphyrins.

Electrochemical Atomic Force Microscopy and First-Principles Calculations of Ferriprotoporphyrin Adsorption and Polymerization.

The adsorption and subsequent electrooxidative polymerization of ferriprotoporphyrin IX chloride (hemin; FePPCl) was investigated on highly ordered pyrolytic graphite, glassy carbon, and polycrystalline Pt electrodes using electrochemical atomic force microscopy, first-principles calculations, and cyclic voltammetry. Hemin was shown to readily adsorb to all three surfaces; however, it was more continuous over the carbon surfaces compared to the Pt surface. This disparity in adsorption appears to be a major contributing factor to differences observed between the electrodes following hemin electropolymerization. Despite differences in roughness and morphology, hemin polymerized as a continuous layer over each electrode surface. Periodic density functional theory calculations were used to model FePP (without Cl) on both the Pt(111) and graphite surfaces using the vdW-DF-optPBE functional to account for the dispersion interactions. Our calculations suggest that the FePP molecule chemisorbs to the Pt surface while at the same time exhibiting intramolecular hydrogen bonding between the carboxylic acid groups, which are extended away from the surface. In contrast to FePP-Pt chemisorption, FePP was found to physisorb to graphite. The preferred spin state upon adsorption was found to be S = 2 on Pt(111), whereas on graphite, the high and intermediate spin states were nearly isoenergetic. Additionally, gas-phase calculations suggest that much of the surface roughness observed microscopically for the polymerized porphyrin layer may originate from the nonparallel stacking of porphyrin molecules, which interact with each other by forming four intermolecular hydrogen bonds and through dispersion interactions between the stacked porphyrin rings. Regardless of polymer thickness, the underlying electrode appears to be able to participate in at least some redox processes. This was observed for the hemin-polymerized Pt electrode using the 2H+/H2 redox couple and was suspected to be due to some Pt surface atoms not being specifically coordinated to the hemin molecules and therefore available to react with H+ that was small enough to diffuse through the polymer layer.

An Isolated Molecule of Iron(II) Phthalocyanin Exhibits Quintet Ground-State: A Nexus between Theory and Experiment.

Iron(II) phthalocyanine (FePc) is an important member of the phthalocyanines family with potential applications in the fields of electrocatalysis, magnetic switching, electrochemical sensing, and phototheranostics. Despite the importance of electronic properties of FePc in these applications, a reliable determination of its ground-state is still challenging. Here we present combined state of the art computational methods and experimental approaches, that is, Mössbauer spectroscopy and Superconducting Quantum Interference Device (SQUID) magnetic measurements to identify the ground state of FePc. While the nature of the ground state obtained with density functional theory (DFT) depends on the functional, giving mostly the triplet state, multi-reference complete active space second-order perturbation theory (CASPT2) and density matrix renormalization group (DMRG) methods assign quintet as the FePc ground-state in gas-phase. This has been confirmed by the hyperfine parameters obtained from 57 Fe Mössbauer spectroscopy performed in frozen monochlorobenzene. The use of monochlorobenzene guarantees an isolated nature of the FePc as indicated by a zero Weiss temperature. The results open doors for exploring the ground state of other metal porphyrin molecules and their controlled spin transitions via external stimuli.

Temperature dependent electron transport and inelastic electron tunneling spectroscopy of porphyrin molecular junctions

Abstract We report electron transport measurements through a metal-molecule-metal junction of free base or zinc porphyrin molecules. Junctions are formed by zig-zag electromigration of a gold nanowire. Inelastic electron tunneling spectroscopy measurements were performed at 4.3 K to confirm the presence of molecules in the junction and to measure the vibrational modes of the molecular junction. Temperature dependent current/voltage measurements are performed in order to determine that the electron conduction mechanism through these molecular junctions is direct tunneling. The electron attenuation coefficient ( β 0 ) was also calculated; the average β 0 for free base and zinc porphyrin was 0.231 ± 0.133 A−1 and 0.188 ± 0.049 A−1, respectively. The barrier height was experimentally found to be 1.6 eV and 1.1 eV for FBP and Zn-P SAMs on Au, respectively.

First-principles study on vibrationally resolved fluorescence of fused 5,15-(diphenyl)-10,20-(dibromo)porphyrin molecule.

The vibrationally resolved fluorescence spectrum of a narrow-line single-molecule transducer, fused 5,15-(diphenyl)-10,20-(dibromo)porphyrin (fused-H2P) molecule, has been calculated by time-dependent density functional theory with the inclusion of both Franck-Condon and Herzberg-Teller contributions. Analytical transition dipole derivatives are used for the calculations of Herzberg-Teller terms to eliminate the possible errors caused by numerical differentials. The performance of different exchange-correlation functionals including B3LYP, ωB97X-D, and M06-2X has been examined. The comparison with the high-resolution experimental emission spectrum indicates that all three functionals can satisfactorily describe the fluorescence spectral profile, while ωB97X-D and M06-2X give slightly better excitation energy than B3LYP. Detailed analysis shows that the fluorescence spectrum is dominated by the Franck-Condon contribution, while the Herzberg-Teller term contributes mostly to its low energy tail. It is found that the size of the basis set has limited influence on the fluorescence spectrum, and a standard 6-31G(d, p) basis set is adequate for the purpose. The substitution of terthiophene side chains is found to have minor effects on the fluorescence spectrum. Our study provides unambitious assignments for all the vibronic structures in the experimental spectrum.

(Zn2Al-LDH/ZnTPPS)n composite films with notable third-order optical nonlinearities

New inorganic-organic transparent composite films of the formula (Zn[Formula: see text]Al-LDH/ZnTPPS)[Formula: see text] were fabricated using exfoliated cationic Zn[Formula: see text]Al layered double hydroxide (Zn[Formula: see text]Al-LDH) nanosheets and anionic meso-tertra(4-sulfophenyl) zinc porphyrin (ZnTPPS) through an electrostatic layerbylayer self-assembly method. The resulting composite films were characterized by UV-vis spectroscopy (UV-vis) scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results showed that the films have relatively smooth and orderly surfaces, with the large ring plane of the porphyrin molecules vertically aligned LDH nanosheets and can grow in a nearly linear fashion with increasing the deposition cycles. Z-scan measurements, which were conducted under laser irradiation at a wavelength of 532 nm pulse width of 6 ns, repetition rate of 10 Hz and light intensity at focus [Formula: see text] of 10 [Formula: see text]J, revealed that the composite films have notable saturation absorption (cf., ZnTPPS in solution shows reverse saturation) and optical nonlinear self-defocusing behavior with the nonlinear optical absorption coefficient [Formula: see text] refractive index [Formula: see text], and third-order NLO susceptibility [Formula: see text] of the films increasing with the increase in number of layers of films ([Formula: see text] value is up to 7.86 × 10[Formula: see text] esu when [Formula: see text] 40), implying the NLO responses could be modified by fine tuning the thickness of composite films.

Crystal structure of (methanol-κO)[5,10,15,20-tetra-kis-(2-amino-phen-yl)porphyrinato-κ4N]zinc(II)-chloro-form-methanol (1/1/1).

In the crystal structure of the title compound, [Zn(C44H32N8)(CH3OH)]·CHCl3·CH3OH, the ZnII cation is coordinated by four porphyrin N and one methanol O atom within a slightly distorted square-pyramidal environment and is shifted out of the porphyrin plane towards the direction of the methanol mol-ecule. The methyl group of the coordinating methanol mol-ecule is disordered over two sets of sites. The porphyrin backbone is nearly planar and the phenyl rings are almost perpendicular to the porphyrin plane. As is typical for picket-fence porphyrins, all four ortho substituents of the meso-phenyl groups (here the amino groups) are facing to the same side of the porphyrin mol-ecule. In the crystal structure, two neighbouring porphyrin complexes form centrosymmetric dimers that are connected via O-H⋯N hydrogen bonding. With the aid of additional N-H⋯N and C-H⋯N hydrogen bonding, these dimers are stacked into columns parallel to [010] that are finally arranged into layers parallel to (001). Between these layers channels are formed where chloro-form solvent mol-ecules are located that are connected to the porphyrin complexes by weak C-H⋯Cl hydrogen bonding. There are additional cavities in the structure where some small residual electron density is found, indicating the presence of disordered methanol mol-ecules, but a reasonable model could not be refined. Therefore the contribution of the electron density associated with the methanol solvent mol-ecule was removed with the SQUEEZE procedure [Spek (2015 ▸). Acta Cryst. C71, 9-18] in PLATON. Nevertheless, the given chemical formula and other crystal data take into account the methanol solvent mol-ecule.