一种合成四(4-N,N-二甲胺基苯基)卟啉的新方法

提出了一种四(4-N,N-二甲胺基苯基)卟啉合成的新方法.该法以氮气为载气携带吡咯蒸气向反应体系中引入定量吡咯,通过降低体系中吡咯浓度,抑制部分副反应,达到提升卟啉合成产率的目的.在研究催化剂用量和反应温度对产物产率影响的基础上,确定了最优化条件:在130℃,二氯乙酸为催化剂,4-N,N-二甲胺基苯甲醛与催化剂的物质的量比为37.3时,四(4-N,N-二甲胺基苯基)卟啉的产率可高达57.0%,这是目前该卟啉最高的合成产率报道.     

Self-assembly of uncharged amphiphilic porphyrins and incorporation of C60 fullerenes in water

We synthesised an uncharged amphiphilic porphyrin, meso-tetrakis-(3,5-di-{2-[2-(2-methoxy-ethoxy)-ethoxy]-ethoxy}-phenyl)-porphyrin, and investigated the supramolecular self-assembly of the porphyrins and the incorporation of C₆₀ molecules into the assembly in aqueous solutions. Spectroscopic and dynamic light scattering studies on the assembly of the amphiphilic porphyrin support that the amphiphilic porphyrins are likely held together through enhanced π–π interactions by pronounced hydrophobic effects in aqueous solutions. It was also found that C₆₀ molecules are efficiently incorporated into the assembly. The fluorescence emitted from the porphyrin ring of the porphyrin/C₆₀ co-assembly in aqueous solution is largely quenched, implying the presence of strong electronic interactions between C₆₀ and porphyrin molecules in the supramolecular assembly.     

Two self-assembled supramolecular solar cells sensitized via axial coordination with zinc porphyrin

In this work, two new self-assemblies based on zinc porphyrins substituted at the meso-positions with different donor units (denoted as ZnP1 and ZnP2) and anchor porphyrin (ZnPA) dyads formed by the coordination bonds of Zn-to-ligand have been prepared. Further, the assemblies were absorbed on semiconducting TiO₂ electrode surfaces by the carboxylic groups of anchor porphyrin (ZnPA), and their photovoltaic performances in solar cells were performed under 100 mW cm^?2 AM 1.5G sunlight. Photoelectrochemical studies reveal a significantly improved photovoltaic behavior for the dyad of triphenylamine-based zinc porphyrin (ZnP1) compared to the dyad with trimethylamine-based zinc porphyrin. The results were verified by electrochemical impedance spectroscopy, calculations, and optical performance. In addition, the modes of the assemblies immobilized on TiO₂ electrode surfaces were also verified by transmission electron microscopy.     

Immobilization of porphyrins in poly(hydroxymethylsiloxane)

Three tetracationic porphyrins differing in the position of charged nitrogen atoms on the peripheral substituents — 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP4), 5,10,15,20-tetrakis(N-methylpyridinium-2-yl)porphyrin (TMPyP2), 5,10,15,20-tetrakis(4-trimethylammoniophenyl) porphyrin (TMAPP), and hydrophobic 5,10,15,20-tetraphenylporphyrin (TPP), were immobilized by adsorption and encapsulation in poly(hydroxymethylsiloxane) (PHOMS). The so prepared porphyrin-PHOMS composites were characterized by porosimetry, scanning electron microscopy, fluorescence and diffuse reflectance UV-VIS spectroscopy. It was found that porphyrins are immobilized in the PHOMS matrix in the free base monomer form Their irradiation produced singlet oxygen O₂(¹Δ_g) with the lifetime of 10–30 μs.     

Study on inclusion complexes of meso-tetrakis(2-thienyl)porphyrin and Cu-meso-tetrakis(2-thienyl)porphyrin with cyclodextrins by spectroscopy method

In phosphate buffer solution of pH5.4, the interaction of meso-tetrakis(2-thienyl)porphyrin(H₂TTP) and Cu-meso-tetrakis(2-thienyl)porphyrin(Cu-TTP) with α-cyclodextrin(α-CD), β-CD, γ-CD, heptakis(2,3,6-tri-O-methyl)-β-CD(TM-β-CD) has been studied by means of UV-vis, fluorescence and ¹HNMR spectroscopy, respectively. The H₂TTP and Cu-TTP can form 1:2 inclusion complexes with TM-β-CD and 1:1 inclusion complexes with the other three cyclodextrins. In this paper, the inclusion constants (K) of H₂TTP and Cu-TTP for the formation of the inclusion complexes have been estimated from the changes of absorbance and fluorescence intensity in phosphate buffer solution. The inclusive capabilities of different kinds of cyclodextrins are compared. The result shows that the inclusion ability of α-CD with H₂TTP and Cu-TTP is the strongest among the three native CDs. The inclusion ability of modified β-CD with H₂TTP and Cu-TTP is stronger, compared to the native β-CD, which indicates that the capacity matching plays a crucial role in the inclusion procedure except for the hydrophobic effect. In addition ¹HNMR spectra supports the inclusion conformation of the TM-β-CD-Cu-TTP inclusion complex, indicating the interaction mechanism of inclusion processes.     

Photocatalytic CO2 Reductions Catalyzed by meso-(1,10-Phenanthrolin-2-yl)-Porphyrins Having a Rhenium(I) Tricarbonyl Complex

We have prepared Zn and free-base porphyrins appended with a fac-Re(phen)(CO)₃Br (where phen is 1,10-phenanthroline) at the meso position of the porphyrin, and performed photocatalytic CO₂ reduction using porphyrin–Re dyads in the presence of either triethylamine (TEA) or 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) as an electron donor. The Zn porphyrin dyad showed a high turnover number for CO production compared with the free-base porphyrin dyad, suggesting that the central Zn ion of porphyrin plays an important role in suppressing electron accumulation on the porphyrin part and achieving high durability of the photocatalytic CO₂ reduction using both TEA and BIH. The effect of acids on the CO₂ reduction was investigated using the Zn porphyrin–Re dyad and BIH. Acetic acid, a relatively strong Brønsted acid, rapidly causes the porphyrin's color to fade upon irradiation and dramatically decreases CO production, whereas proper weak Brønsted acids such as 2,2,2-trifluoroethanol and phenol enhance the CO₂ reduction.     

Spectroscopic Investigations of Porphyrin-TiO2 Nanoparticles Complexes

This study presents the spectral characterization of TiO₂ nanoparticles (NPs) functionalized with three porphyrin derivatives: 5,10,15,20-(Tetra-4-aminophenyl) porphyrin (TAPP), 5,10,15,20-(Tetra-4-methoxyphenyl) porphyrin (TMPP), and 5,10,15,20-(Tetra-4-carboxyphenyl) porphyrin (TCPP). UV-Vis absorption and Fourier transform infrared spectroscopy–attenuated total reflection (FTIR-ATR) spectroscopic studies of these porphyrins and their complexes with TiO₂ NPs were performed. In addition, the efficiency of singlet oxygen generation, the key species in photodynamic therapy, was investigated. UV-Vis absorption spectra of the NPs complexes showed the characteristic bands of porphyrins. These allowed us to determine the loaded porphyrins on TiO₂ NPs functionalized with porphyrins. FTIR-ATR revealed the formation of porphyrin-TiO₂ complexes, suggesting that porphyrin adsorption on TiO₂ may involve the pyrroles in the porphyrin ring, or the radicals of the porphyrin derivative. The quantum yield for singlet oxygen generation by the studied porphyrin complexes with TiO₂ was higher compared to bare porphyrins for TAPP and TMPP, while for the TCPP-TiO₂ NPs complex, a decrease was observed, but still maintained a good efficiency. The TiO₂ NPs conjugates can be promising candidates to be tested in photodynamic therapy in vitro assays.     

Immobilized manganese porphyrin on functionalized magnetic nanoparticles via axial ligation: efficient and recyclable nanocatalyst for oxidation reactions

Magnetic nanoparticles (MNPs), Fe₃O₄@SiO₂, have been prepared and functionalized by 3-(chloropropyl)trimethoxysilane and then by imidazole to synthesize Fe₃O₄@SiO₂-Im. The functionalized Fe₃O₄ nanoparticles were used as a support to anchor manganese porphyrin via axial ligation. The prepared catalyst was characterized by elemental analysis, FT-IR spectroscopy, X-ray powder diffraction, UV–vis spectroscopy, and scanning electron microscopy. Application of immobilized manganese porphyrin as a heterogeneous catalyst in oxidation of alkenes and sulfides was explored. To find suitable reaction conditions, effect of different parameters such as solvent and temperature on immobilization process and also various reaction parameters (oxidant, solvent, and time) on oxidation reactions has been investigated. The results showed that the immobilized Mn-porphyrin on functionalized MNPs is an efficient and reusable catalyst for oxidation of substrates.     

Centrally Coordinated Cobalt Porphyrin Monolayers on the Surface of TiO2 Nanoparticles

Aminopropyltrimethoxysilane (APTS) on the surface of TiO₂ nanoparticles was used to bind cobalt(II) 5,10,15,20-tetra-(4-trimethylaminophenyl)porphyrin iodide (CoTAPPI). The binding involved coordination of amino-group in the APTS to cobalt(II) ion in the center of the porphyrin. The absorption and fluorescence spectra of the products showed that there existed the electron transfer among TiO₂, APTS, and CoTAPPI. The polarized fluorescence spectra were used to evaluate the coordination constants of the porphyrin and APTS. The molecular geometry and binding energy of the TiO₂-APTS-CoTAPPI assembly were calculated with the molecular mechanics approach (MM2).     

Synthesis and cytotoxicity study of gold(III) porphyrin complexes and their derivative in breast cancer cells

Gold(III) [Au(III)] complexes exhibit potential anticancer activities. A series of Au(III) porphyrin complexes containing different meso-substituent groups (phenyl, methoxyphenyl, butyloxyphenyl, octyloxyphenyl, and decyloxyphenyl) was synthesized. The synthesized compounds were characterized using mass spectrometry, infrared spectroscopy, UV–visible and fluorescence spectroscopy, and electron paramagnetic resonance spectroscopy. Moreover, the in vitro cytotoxicity of these Au(III) porphyrin complexes was investigated using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide surrogate viability assay on an MCF7 human breast cancer cell line. The Au(III) complexes with 5,10,15,20-tetraphenylporphyrin (AuTPP) and 5,10,15,20-tetrakis(4-methyloxyphenyl)porphyrin (AuTOMPP) demonstrated high anticancer activity with IC₅₀ values against MCF7 cells at 4.30 and 25.35 µM, respectively. The toxicity of the Au(III) porphyrin complexes against the LLC-MK2 rhesus monkey kidney epithelial cell line, a representative normal cell line, was investigated. All the tested Au(III) porphyrin complexes were non-cytotoxic in LLC-MK2 cells. For AuTPP, more than 80% LLC-MK2 cell viability was observed at concentrations lower than 5 μM.     

Synthesis of chiral water-soluble metalloporphyrins (Fe, Ru,): new catalysts for asymmetric carbene transfer in water

The reaction of optically active Halterman porphyrin with sulfuric acid (95%) provided the expected water-soluble para-tetrasulfonated porphyrin in 82% yield. The metalloporphyrin complexes were prepared by metal insertion (iron) or direct sulfonation of the chiral ruthenium porphyrin. The asymmetric addition of diazoacetate to styrene to give optically active trans cyclopropyl ester (ee up to 86%) was carried out in water by using chiral iron or ruthenium porphyrins with a possible reuse due to the high solubility and stability in aqueous solution.     

Structure and redox properties of electropolymerized film obtained from iron meso‐tetrakis(3‐thienyl)porphyrin

Oxidative polymerization of bromoiron(III) meso‐tetrakis(3‐thienyl)porphyrin gave a novel polymeric porphyrin complex randomly crosslinked at the 2,5‐positions of the peripheral thienyl groups. The electrical semiconductivity of ca. 10^?5 S/cm after I₂ doping indicated that the polymer had a π‐conjugated structure with a moderate delocalization of π electrons over the thienylporphyrin units. PM3 calculations for free‐base models revealed that HOCO (the highest occupied crystal orbital) band width was reduced by introduction of the porphyrin moieties into the thienylene backbone and yet low HOCO‐LUCO (the lowest unoccupied crystal orbital) gap was maintained, which accounted for the relatively low electrical conductivity of the porphyrin polymer. The modified electrode prepared by electropolymerization was redox‐active due to the presence of iron(II/III) couple and the semiconductivity of the film, which served as a novel non‐enzymatic electrochemical sensor for superoxide anion radical based on the facile electrocatalytic oxidation of the superoxide. Copyright © 2005 John Wiley & Sons, Ltd.     

Photochemical hydrogen production with molecular devices comprising a zinc porphyrin and a cobaloxime catalyst

Two new noble-metal-free molecular devices,[{Co(dmgH) 2 Cl}{Zn(PyTPP)}](1,dmgH = dimethyloxime,PyTPP = 5-(4pyridyl)-10,15,20-triphenylporphyrin) and [{Co(dmgH) 2 Cl}{Zn(apPyTPP)}](2,apPyTPP = 5-[4-(isonicotinamidyl)phenyl]10,15,20-triphenylporphyrin),for light-driven hydrogen generation were prepared and spectroscopically characterized.The zinc porphyrin photosensitizer and the Co III-based catalyst unit are linked by axial coordination of a pyridyl group in the periphery of zinc-porphyrin to the cobalt centre of catalyst with different lengths of bridges.The apparent fluorescence quenching and lifetime decays of 1 and 2 were observed in comparison with their reference chromophores,Zn(PyTPP)(3) and Zn(apPyTPP)(4),suggesting a possibility for an intramolecular electron transfer from the singlet excited state of zinc porphyrin unit to the cobalt centre in the molecular devices.Photochemical H2-evolving studies show that complexes 1 and 2 are efficient molecular photocatalysts for visible light-driven H2 generation from water with triethylamine as a sacrificial electron donor in THF/H2 O,with turnover numbers up to 46 and 35 for 1 and 2,respectively.In contrast to these molecular devices,the multicomponent catalyst of zinc porphyrin and [Co(dmgH) 2 PyCl] did not show any fluorescence quenching and as a consequence,no H2 gas was detected by GC analysis in the presence of triethylamine with irradiation of visible light.The plausible mechanism for the photochemical H2 generation with these molecular devices is discussed.     

Convergent synthesis of meso-ferrocenyl porphyrins for TiO2 sensitization

Electron-donating ferrocenyl moieties have been incorporated into supramolecular carboxyporphyrin architectures Zn(II)-5-ferrocenyl-10,20-bistolyl-15-(4-methylbenzoate)porphyrin (trans-Fc-ZnP-CO₂Me), Zn(II)-5-ferrocenyl-10,15,20-tris(4-methylbenzoate)porphyrin [trans-Fc-ZnP-(CO₂Me)₃], and Zn(II)-5,15-bisferrocenyl-10,20-bis(4-benzoate)porphyrin [trans-Fc₂-ZnP-(CO₂Me)₂] for self-assembly on metal oxide nanoparticles. Efficient and economic synthesis has required a convergent strategy toward reduced symmetry trans-A₂B₂ and trans-AB₂C substitution patterns about the porphyrin macrocycle minimizing the production of porphyrin side products and increasing yields of the target ferrocenylporphyrins. Preliminary spectroscopic data in solution and in the solid state bound to mesoporous TiO₂ films are discussed.     

Isolating Fe-O2 Intermediates in Dioxygen Activation by Iron Porphyrin Complexes

Dioxygen (O₂) is an environmentally benign and abundant oxidant whose utilization is of great interest in the design of bioinspired synthetic catalytic oxidation systems to reduce energy consumption. However, it is unfortunate that utilization of O₂ is a significant challenge because of the thermodynamic stability of O₂ in its triplet ground state. Nevertheless, nature is able to overcome the spin state barrier using enzymes, which contain transition metals with unpaired d-electrons facilitating the activation of O₂ by metal coordination. This inspires bioinorganic chemists to synthesize biomimetic small-molecule iron porphyrin complexes to carry out the O₂ activation, wherein Fe-O₂ species have been implicated as the key reactive intermediates. In recent years, a number of Fe-O₂ intermediates have been synthesized by activating O₂ at iron centers supported on porphyrin ligands. In this review, we focus on a few examples of these advances with emphasis in each case on the particular design of iron porphyrin complexes and particular reaction environments to stabilize and isolate metal-O₂ intermediates in dioxygen activation, which will provide clues to elucidate structures of reactive intermediates and mechanistic insights in biological processes.     

Synthesis of Novel Porphyrin Derivatives with Mesogenic Properties

Two novel porphyrin derivatives, 5,10,15,20-tetra(4-(N-octane-carboxamide)phenyl)porphyrin (4NC₈-TPP) and 5,10,15,20-tetra(4-(N-stearyl-carboxamide)phenyl)porphyrin (4NC₁₈-TPP), were synthesized. Their molecular structures were characterized by means of time-of-flight mass spectrometer (TOF-MS), nuclear magnetic resonance (NMR), and infrared spectra (IR). The thermal behavior and morphologies of 4NC₈-TPP and 4NC₁₈-TPP were examined by thermal gravity (TG), differential scanning calorimetry (DSC), x-ray diffraction (XRD), and polarizing optical microscope (POM). It was found that both 4NC₈-TPP and 4NC₁₈-TPP had mesogenic properties.     

Polypyridylpropyne‐Pd and ‐Pt porphyrin coating for visualization of oxygen pressure

Poly[1‐trimethylsilyl‐1‐propyne‐co‐1‐(3‐pyridyl)propyne] 1 was prepared both as a polymer‐ligand of a palladium porphyrin (PdOEP) and of a platinum porphyrin (PtTFP) and as a highly gas‐permeable polymer matrix of the porphyrin. The porphyrin acted as a phosphorescence probe which could be quenched with oxygen and sense the oxygen partial pressure. 1 gave a smooth and tough coating with a thickness of ca. 2 µm which homogeneously involved the porphyrin. The porphyrin‐ 1 coatings displayed strong red‐colored phosphorescences (the emission maximum at 670 and 650 nm for PdOEP and PtTFP, respectively), and their intensity significantly decreased with an increase in the oxygen partial pressure on the coating. The high oxygen‐quenching efficiency or the high oxygen pressure sensitivity of the porphyrin's phosphorescence was observed even at cryogenic temperature. Aggregation of the porphyrin was suppressed in the coating by ligation of the porphyrin with the nitrogenous residue of 1 to significantly reduce spatial noise in the phosphorescence measurement or the oxygen‐pressure sensing. PtTFP‐ 1 was coated on the surface of a delta wing model. The oxygen‐pressure distribution on the coated model was successfully visualized in a cryogenic wind tunnel test. Copyright © 2008 John Wiley & Sons, Ltd.     

Controlled Synthesis of meso‐Veratrylporphyrins under Acid‐Catalyzed Scrambling Conditions

5,15‐Bis(veratryl)porphyrin (1), 5,10,15‐tris(veratryl)porphyrin (2), and 5,10,15,20‐tetrakis(veratryl)porphyrin (3), C₃₆H₃₀N₄O₄, C₄₄H₃₈N₄O_6, and C₅₂H₄₆N₄O₈ were synthesized by an acid‐catalyzed, one‐pot reaction of meso‐dipyrromethane, 3,4‐di‐OCH₃‐benzaldehyde (veratraldehyde), and trifluoroacetic acid (TFA). These three different products were obtained as a result of scrambling reactions. The molecular structures have been characterized by elemental analysis, ESI mass spectra, 1D and 2D NMR techniques (¹H and ¹³C), and UV‐visible spectroscopy.     

Porphyrin derivatives act as vinylene monomers in TEMPO‐mediated radical copolymerization with styrene

In this article, we offer clear evidence for the radical copolymerizability of porphyrin rings in 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO)‐mediated radical copolymerizations with styrene. The radical copolymerizations of styrene with 5,10,15,20‐tetrakis(pentafluorophenyl)porphyrin (H₂TFPP) was conducted using 1‐phenyl‐1‐(2,2,6,6‐tetramethyl‐1‐piperidinyloxy)ethane as an initiator. The refractive index (RI) traces for the size‐exclusion chromatography of the resulting copolymers were unimodal with narrow molecular weight distributions. The RI traces shifted toward higher molecular weight regions as the polymerization progressed, and the number‐average molecular weights were close to those calculated on the basis of the feed compositions and monomer conversions. These features were in good agreement with a TEMPO‐mediated mechanism. The traces recorded by the ultraviolet‐visible (UV‐vis) detector (430 nm) were identical to those obtained by the RI detector, indicating a statistical copolymerization of styrene with H₂TFPP. This also indicated that H₂TFPP acted as a monomer and not as a terminator or a chain‐transfer agent under the conditions used. A benzyl radical addition to H₂TFPP was conducted as a model reaction for the copolymerization using tributyltin hydride as a chain‐transfer agent, affording a reduced porphyrin, 2‐benzyl‐5,10,15,20‐tetrakis(pentafluorophenyl)chlorin 1 , via radical addition to the β‐pyrrole position. The UV‐vis spectrum of 1 was fairly similar to that of poly(styrene‐co‐H₂TFPP), indicating that H₂TFPP polymerized at its β‐pyrrole position in the TEMPO‐mediated radical polymerization. TEMPO‐mediated radical copolymerizations of styrene with several porphyrin derivatives were also demonstrated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of Extremely π‐Extended Porphyrin Tapes from Hybrid meso‐meso Linked Porphyrin Arrays: An Approach Towards the Conjugation Length

Directly meso‐meso, β‐β, β‐β triply linked porphyrin arrays are exceptional π‐conjugated molecules exhibiting remarkably red‐shifted absorption bands extending deeply in the IR region. In order to determine the effective conjugated length (ECL), we embarked on the synthesis of the porphyrin tapes far beyond the 12‐mer, which is the longest we have prepared so far. In this study, to find the compromise between the feasibility of the meso‐meso coupling reaction up to longer arrays and the sufficient solubility and chemical stability of the resultant porphyrin tapes, we prepared hybrid meso‐meso linked porphyrin arrays BOn up to 24‐mer, which have two different aryl groups, a 2,4,6‐tris(3,5‐di‐tert‐butylphenoxy) phenyl group (Ar¹) and a 3,5‐dioctyloxy phenyl group (Ar²). All these arrays were effectively converted into the corresponding triply linked porphyrin tapes TBOn by oxidation with DDQ‐Sc(OTf)₃. Importantly, the low energy Q‐band‐like absorption bands of TBOn are progressively red‐shifted with an increase in the number of porphyrins n until 16 but the red‐shift is saturated at n=16, indicating the ECL of the porphyrin tape to be around 14–16. The regularly introduced meso‐aryl bulky substituents impose facial encumbrance, hence leading to the effective suppression of π–π interactions as well as improvement of the chemical stabilities of TBOn .