55253-62-8

Usage

Uses

Used in Medical Applications:
(α,α,α,α)-5,10,15,20-tetrakisphenyl>-21H,23H-porphine is used as a diagnostic imaging agent for its ability to interact with light in a manner that can be detected and visualized, aiding in the identification of various medical conditions.
(α,α,α,α)-5,10,15,20-tetrakisphenyl>-21H,23H-porphine is also used as a photosensitizer in photodynamic therapy, where its interaction with light can generate reactive oxygen species to target and destroy diseased cells, particularly in cancer treatment.
Used in Material Science:
In the field of material science, (α,α,α,α)-5,10,15,20-tetrakisphenyl>-21H,23H-porphine is used as a component in organic electronics due to its electronic properties and potential for molecular engineering.
(α,α,α,α)-5,10,15,20-tetrakisphenyl>-21H,23H-porphine is used in the development of solar cells for its light-harvesting capabilities and potential to improve the efficiency of energy conversion.
Used in Research:
(α,α,α,α)-5,10,15,20-tetrakisphenyl>-21H,23H-porphine serves as a valuable research tool for studying molecular interactions, photophysical processes, and the development of new methodologies in synthetic chemistry and molecular biology.

Upstream product

• 52199-35-6 tetrakis-5,10,15,20-(o-aminophenyl)porphyrin 
• 3282-30-2 pivaloyl chloride 
• 920-46-7 Methacryloyl chloride 
• 75-98-9 Trimethylacetic acid 
• 552-89-6 2-nitro-benzaldehyde 
• 37116-82-8 5,10,15,20-tetrakis(o-nitrophenyl)porphyrin 

Downstream Products

• 120120-01-6 nickel(II) meso-α,α,α,α-tetrakis(o-pivalamidophenyl)porphyrin 
• 53675-31-3 [meso-β-(o-pivalamidophenyl)-α,α,α-tris(o-pivalamidophenyl)porphinato] cobalt(II) 

Relevant academic research and scientific papers

Controlling Oxygen Reduction Selectivity through Steric Effects: Electrocatalytic Two-Electron and Four-Electron Oxygen Reduction with Cobalt Porphyrin Atropisomers

Achieving a selective 2 e? or 4 e? oxygen reduction reaction (ORR) is critical but challenging. Herein, we report controlling ORR selectivity of Co porphyrins by tuning only steric effects. We designed Co porphyrin 1 with meso-phenyls each bearing a bulky ortho-amido group. Due to the resulted steric hinderance, 1 has four atropisomers with similar electronic structures but dissimilar steric effects. Isomers αβαβ and αααα catalyze ORR with n=2.10 and 3.75 (n is the electron number transferred per O2), respectively, but ααββ and αααβ show poor selectivity with n=2.89–3.10. Isomer αβαβ catalyzes 2 e? ORR by preventing a bimolecular O2 activation path, while αααα improves 4 e? ORR selectivity by improving O2 binding at its pocket, a feature confirmed by spectroscopy methods, including O K-edge near-edge X-ray absorption fine structure. This work represents an unparalleled example to improve 2 e? and 4 e? ORR by tuning only steric effects without changing molecular and electronic structures.

Homolytic versus Heterolytic Hydrogen Evolution Reaction Steered by a Steric Effect

Several H?H bond forming pathways have been proposed for the hydrogen evolution reaction (HER). Revealing these HER mechanisms is of fundamental importance for the rational design of catalysts and is also extremely challenging. Now, an unparalleled example of switching between homolytic and heterolytic HER mechanisms is reported. Three nickel(II) porphyrins were designed and synthesized with distinct steric effects by introducing bulky amido moieties to ortho- or para-positions of the meso-phenyl groups. These porphyrins exhibited different catalytic HER behaviors. For these Ni porphyrins, although their 1e-reduced forms are active to reduce trifluoroacetic acid, the resulting Ni hydrides (depending on the steric effects of porphyrin rings) have different pathways to make H2. Understanding HER processes, especially controllable switching between homolytic and heterolytic H?H bond formation pathways through molecular engineering, is unprecedented in electrocatalysis.

Effect of an Oxygen-Binding Reaction at the Cobalt Porphyrin Site Fixed in a Polymer Membrane on Facilitated Oxygen Transport

Oxygen transport was facilitated in polymer membranes bonded with new derivatives of cobalt (CoPs).The oxygen- binding reactivity of fixed CoPs strongly influenced the facilitated oxygen transport.CoP

Chemically Specific Surface Diffusion of Oxygen through a Porous Membrane Modified with Cobalt Porphyrin on Its Pore Surface

Chemically specific surface diffusion of oxygen was observed on a porous glass membrane modified on its pore surface with cobalt porphyrin (CoP) which binds oxygen specifically and reversibly from air.The membrane displayed both permselectivity for oxygen

Cobalt Porphyrin-Mediated Oxygen Transport in a Polymer Membrane: Effect of the Cobalt Porphyrin Structure on the Oxygen-Binding Reaction, Oxygen-Diffusion Constants, and Oxygen-Transport Efficiency

New derivatives of (meso-α,α,α,α-tetrakis(o-pivalamidophenyl)porphinato)cobalt (CoPs) were characterized by oxygen-binding equilibrium and rate constants of the cobalt centered in the porphyrins.They depended on the structure of the porphyrin; for example, the rate constants of oxygen binding and dissociation (kon and koff) for α3β-CoP4P (Chart 1) were 3 and 20 times as large as those for α4-CoB4P, respectively.Oxygen transport through the polymer membranes containing CoPs as the fixed oxygen carriers was facilitated and was affected by the oxygen-binding character or the structure of CoPs.The logarithmically linear correlation of the oxygen-dissociation rate constant of CoPs (koff = (3-66)E3 s-1) with the diffusion constant of oxygen via CoPs fixed in the membranes (Dcc = (3-140)E-9 cm2 s-1) was given for those six CoP derivatives.

Demetalation of (5,10,15,20-Tetraphenylporphyrinato)iron Complexes: Effect of Substituents at the o-Positions of Phenyl Groups

The demetalation of a series of (5,10,15,20-tetraphenylporphyrinato)iron(III) complexes having bulky substituents at the o-positions of phenyl rings was studied in acetic acid in the presence of iron(II) chloride and HCl.The reaction occurred simultaneously with the reduction of Fe(III) porphyrin to Fe(II) porphyrin, since no demetalation was observed without iron(II) chloride.The pseudo-first-order rate constants, which were determined spectrophotometrically, decreased with an increase in the bulkiness of the o-substituents on the phenyl rings.The atropisomeric structures of the products were determined by high-resolution NMR measurements.

Atropisomer-Specific Formation of Premicellar Porphyrin J-Aggregates in Aqueous Surfactant Solutions

The 4,0-atropisomer of intermediate (C6 or C7) to long (C16) chain length picket fence porphyrins (PFPs) exhibit red-shifted absorption and reduced singlet and triplet lifetimes in dilute aqueous surfactant solutions (i.e. below the critical micelle conce

Bis-Benzimidazole-Appended Binucleating Porphyrin Ligands: Synthesis, Characterization, and X-ray Structure

The synthesis and characterization of some new binucleating tetraarylporphyrin ligands is reported.The potentially most useful example is α,α,5,15-bis-α,α,10,20-bis(pivalamidophenyl)porphine (8).The ligands have two appended benzimidazole arms which are designed to chelate a second metal directly above the porphyrin.The synthetic methodology for obtaining both the 5,15 (i.e., trans) and the 5,10 (i.e., cis) bis-appended ligand from an α,α,α,α,5,10,15,20 tetra-functionalized starting material is described in detail.A key design feature of the ligand system is amenability to single-crystal X-ray structure determination and this is demonstrated with an X-ray structure of a copper(II) complex.Crystal data for CuC74H66N12O4*1.5(diethyl ether)*toluene are the following: monoclinic, C2/c, a = 31.240 (4) Angstroem, b = 16.769 (5) Angstroem, c = 35.199 (4) Angstroem, β = 121,4 (1) grad; R = 0.0823, Rw = 0.0826.H bonding between the benzimidazole moieties and the pivalamido pickets is seen to determine the structural disposition of the appendages lying above the porphyrin ring.Iron(III) porphyrin complexes of these new ligands exist in a hydroxo monomer form as well as the familiar μ-oxo dimer form.

Physicochemical Properties of the Atropisomers of meso-Tetra(o-pivalamidophenyl)porphyrin

Four possible atropisomers of meso-tetra(o-pivalamidophenyl)porphyrin, one of which is known as the picket fence porphyrin, have been prepared and their physicochemical properties examined.The visible absorption spectra of the isomers are all different, especially in DMF.The wavelength of the absorption maxima is most blue-shifted in the αααα-isomer.Phyllotype tendency, which is characterized by the relative intensity of the four bands in the visible region, was in the order αααα > ααββ ca.= αααβ > αβαβ.This is the same order as that of the blue shift.The order is also the same as that of the reduction potentials measured in DMF.The nuclear magnetic resonance (NMR) chemical shifts of methyl protons of the pivalamido groups are distinguishable among the four isomers even in a mixture of the isomers in chloroform or toluene.These results indicate that the conformation of the porphyrin (the distribution of the pivalamido groups between the two sides of the porphyrin plane) affects the physicochemical properties of the porphyrin.Interaction between adjacent pivalamido groups is considered to be responsible for this phenomenon.Keywords - atropisomer; porphyrin; picket fence porphyrin; reduction potential; UV; NMR.

Models of the Cytochromes b. 4. Effect of Axial Ligand Plane Orientation on the Proton NMR Spectra of Symmetrically Substituted Low-Spin Iron(III) Porphyrins

Mixtures of the αβαβ and ααββ atropisomers of tetrakis(o-pivalamidophenyl)porphyrin, (o-piv)4TPPH2. were separated from the other atropisomers and the ratio determined by NMR techniques.Insertion of iron required extended reflux time, and significant (ca.