In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin-MtTMPyP(Mt= Cobalt(Ⅱ), Manganese(Ⅲ), or Iron(Ⅲ); TMPyP = 5, 10, 15, 20-tetrakis(N-methylpyridiniu...In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin-MtTMPyP(Mt= Cobalt(Ⅱ), Manganese(Ⅲ), or Iron(Ⅲ); TMPyP = 5, 10, 15, 20-tetrakis(N-methylpyridinium-4-yl) porphyrin) intercalated into the layer of graphene oxide(GO) by the cooperative effects of electrostatic and π-π stacking interaction between positively charged metal porphyrin and negatively charged GO sheets. Followed by reduction with hydrazine vapor, a series of novel 2 D MtTMPyP/rGO_n were fabricated. The as-prepared 2 D hybrids were fully characterized and tested as non-noble metal catalysts for oxygen reduction reaction(ORR) in an alkaline medium. The MtTMPyP/rGO_n hybrids, especially CoTMPyP/rGO_5, demonstrated an improved electrocatalytic activity for ORR and a number of exchanged electrons close to 4-electron reaction, increased stability and excellent tolerance to methanol, showing a potential alternative catalyst for ORR in fuel cells and air batteries.展开更多
The reaction of 5, 10, 15, 20-tetra-(4-pyridyl) porphyrin 1 with triruthenium dodecacarbonyl [Ru3(CO)12], zinc(II) acetate, copper(II) acetate, cobalt(II) acetate afforded complexes 2a?2d respectively. Treatment of 2a...The reaction of 5, 10, 15, 20-tetra-(4-pyridyl) porphyrin 1 with triruthenium dodecacarbonyl [Ru3(CO)12], zinc(II) acetate, copper(II) acetate, cobalt(II) acetate afforded complexes 2a?2d respectively. Treatment of 2a?2d with Merrifield’s peptide resin obtained 3a?3d. The compounds 3a?3d reacted with methyl iodide respectively gave 4a?4d. New complexes 4a?4d have been identified by IR, UV-visible spectra, and AES.展开更多
The reaction of pyrrole with 4-hydroxybenzaldehyde and 4-pyridinecarboxaldehyde afforded new porphyrin ligand 1. Treatment of 1 with copper( II ) acetate, cobalt ( II ) acetate gave complexes 2-3 respectively. 2 and 3...The reaction of pyrrole with 4-hydroxybenzaldehyde and 4-pyridinecarboxaldehyde afforded new porphyrin ligand 1. Treatment of 1 with copper( II ) acetate, cobalt ( II ) acetate gave complexes 2-3 respectively. 2 and 3 reacted with Merrifield's peptide resin produced 4 and 5. Complexes 4 and 5 reacted with methyl iodide respectively gave 6-7. The new compounds 1-7 have been identified by H-1 NMR, IR, MS and UV-visible spectra, elemental analysis and AES.展开更多
6-Deoxy- 6-iodo-β-cyclodextrin (1) reacted with 5-(p-aminophenyl)-10, 15,20-triphenyl porphyrin(2), 5-(p-aminophenyl)-10,15,20-triphenyl nickel(Ⅱ) porphyrin [NiⅡTPPNH2P](3),5-(p-aminophenyl)-10,15,20-triphenyl mang...6-Deoxy- 6-iodo-β-cyclodextrin (1) reacted with 5-(p-aminophenyl)-10, 15,20-triphenyl porphyrin(2), 5-(p-aminophenyl)-10,15,20-triphenyl nickel(Ⅱ) porphyrin [NiⅡTPPNH2P](3),5-(p-aminophenyl)-10,15,20-triphenyl manganese(Ⅲ) porphyrin [MnⅢTPPNH2P] (4) and 5-(p-aminophenyl)-10,l5,20-triphenyl carbonyl ruthenium porphyrin [RuⅡ (CO)TPPNH2P] (5) to generate the compounds 6-9, respectively. Those new compound 5-9 have been identified by 1H NMR, IR, MS and UV-visible spectra and elemental analysis.展开更多
The complexes of biogenic metals (Zn2+,Cu2+,Co2+,Mn3+,Fe3+) based on meso-tetra(3,5-diisobor- nyl-4-hydroxyphenyl)porphyrin 1 were synthesized. The electrochemical behavior of these com-pounds was studied using cyclic...The complexes of biogenic metals (Zn2+,Cu2+,Co2+,Mn3+,Fe3+) based on meso-tetra(3,5-diisobor- nyl-4-hydroxyphenyl)porphyrin 1 were synthesized. The electrochemical behavior of these com-pounds was studied using cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. The antioxidant activity of complexes was estimated by means of the electrochemical assay based on the hydrogen atom transfer reaction to the stable radical 2,2’-diphenyl-1-picrylhydrazyl (DPPH). The RDE method was applied for this process monitoring. It was shown that the efficiency of the metal complexes (Cu2+,Co2+,Mn2+,Ni2+,Fe3+) is practically the same order as that of free base porphyrin 1. However the Zn2+ complex demonstrates significantly higher antioxidant activity, and the stoichiometry of the reaction was determined as σ = 4. The results demonstrate that porphyrin macrocycle can directly affect the antioxidant properties of 2,6-diisobornylphenol.展开更多
Reactions of 5-(p-aminophenyl)-10, 15, 20-triphenyl porphyrin (1) withRu_3(CO)_(12) or M(OCOCH_3)_2 (M= Ni, Mn) afforded metalloporphyrins (4―6), respectively.6-Deoxy-6-io-do-β-cyclodextrin (2) and mono (6-O-trifluo...Reactions of 5-(p-aminophenyl)-10, 15, 20-triphenyl porphyrin (1) withRu_3(CO)_(12) or M(OCOCH_3)_2 (M= Ni, Mn) afforded metalloporphyrins (4―6), respectively.6-Deoxy-6-io-do-β-cyclodextrin (2) and mono (6-O-trifluoromethanesulfonyl) pennethylatedβ-cyclodextrin (3) reacted with complexes 4―6 to give β-cyclodextrin bonded metal porphyrins(7―9) and permethylated β-cyclodextrin bonded me-tal porphyrins (10―12) respectively. These newcomplexes were identified by MS, IR, UV-visible and ~1H NMR spectra, and elemental analysis.展开更多
The metal contents of Nigerian coal minerals were analyzed using an atomic absorption spectrophotometer. Calcium, Na, and Fe occurred as the major elements with concentrations ranging from 9 782 μg/g for Ca to 432 μ...The metal contents of Nigerian coal minerals were analyzed using an atomic absorption spectrophotometer. Calcium, Na, and Fe occurred as the major elements with concentrations ranging from 9 782 μg/g for Ca to 432 μg/g for Na whereas K, Mg, Mn, Ni, Cr, Zn, Pb, and Cu, which occurred at trace levels ranged from 673.73 μg/g for Mg to 2.97 μg/g for Mn. The results of the quantitative analysis of porphyrins extracted from the coal minerals showed that Onyeama coal has the highest amount of porphyrins (ca～0.96 μg/g) while Okpara has the lowest (ca～0.30 μg/g). The porphyrins were qualitatively characterized by a combination of thin layer chromatography (TLC), infrared, and ultraviolet-visible spectrophotometers. The results of the mid infrared analysis (MIR) showed the presence of absorption bands at 3 440 cm～1～3 450 cm-1 and 1 640 cm-1～1 680 cm-1 , which are owing to the stretching vibrations of N ─ H and C─ C of aromatics, with C─ H out of plane (oop) bending vibrations at wavenumbers less than 900 cm-1, all of which are characteristic absorptions of porphyrin free base. The ultraviolet-visible data showed prominent peaks at ～400 nm(Soret band) and at wavelength ranges of 535 nm～550 nm(β-band) and 565 nm～ 600 nm (α-band) for the coal porphyrins analyzed. The geochemical significance of the metals and porphyrins in coal minerals are discussed.展开更多
A convenient synthetic method of metal dendritic porphyrins through the convergent synthetic strategy is described. The porphyrin core were linked with the synthetic fragments by forming ether or ester bonds to give f...A convenient synthetic method of metal dendritic porphyrins through the convergent synthetic strategy is described. The porphyrin core were linked with the synthetic fragments by forming ether or ester bonds to give five target compounds were prepared.展开更多
Though the photo-physical properties of free base porphyrin are attractive, there are still problems for the materials with weak and narrow range absorption of visible light. The unsymmetrical neo-confused porphyrin d...Though the photo-physical properties of free base porphyrin are attractive, there are still problems for the materials with weak and narrow range absorption of visible light. The unsymmetrical neo-confused porphyrin derivatives were introduced as novel materials for the improvement of photo-chemical and photo-physical properties. The density function theory（DFT）and time dependent density function theory（TDDFT） were applied to calculate the absorption spectrum of unsymmetrical neo-confused porphyrin（N-CP） and metal-coordinated N-CP in various solutions. The Ni and Zn coordinated neo-confused porphyrin dipole moment values are smaller than the values of prototype porphyrin（Pro P） and N–CP. According to the electrophilicity index ω, Ni coordinated N–CP（Ni–N–CP） is susceptible to the polarity of solvents, while the Zn coordinated derivative（Zn–N–CP） is more immune to the solvent environment. Unlike the Gouterman＇s four frontier orbital model of common porphyrin materials, the electron transitions of N–CPs and metalcoordinated N–CPs from H–2 or lower molecular orbitals also contribute to ultraviolet and visible absorption. Most of oscillator strength f values of Zn–N–CP are significantly higher than the values of Ni–N–CP, which reflects the higher absorption intensity of Q and Soret bands. The maximum wavelength at 702.2 nm in vacuum drew our attention to the novel material. The broad absorption range, intense red-shifted Q band and higher stability in solvents suggest that N–CPs, especially Zn–N–CP, can be one class of new candidate dye-sensitized materials.展开更多
Experimental crystallographic structural parameters of a range of metaled meso-substituted and unsubstituted porphyrins were reviewed to show how far the meso-substitution by any functional group and the insertion of ...Experimental crystallographic structural parameters of a range of metaled meso-substituted and unsubstituted porphyrins were reviewed to show how far the meso-substitution by any functional group and the insertion of metal in the porphyrins core macrocycle may affect the geometry. The analysis of twists and angles has shown two kinds of distortions: external [T(C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-X<sup>n</sup>) and T(C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-C<sup>α</sup>)] and internal [T(N<sup>m</sup>-C<sup>α</sup>-C<sup>meso</sup>-X<sup>n</sup>) and T(N<sup>n</sup>-C<sup>α</sup>-C<sup>meso</sup>-C<sup>α</sup>)] with averages of [+6°and –6°] and [–5°and +5°], respectively. In the meso-substituted case, the external and internal twists C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-X and N-C<sup>α</sup>-C<sup>meso</sup>-X, respectively are oppositely orientated. Similar effect is observed in meso-unsubstituted of C<sup>β</sup>-C<sup>α</sup>- C<sup>meso</sup>-H and N-C<sup>α</sup>-C<sup>meso</sup>-H. However, the external distortions are more significant than internal. Considering the same order, the limit of distortions is [97°and 132°(–48°)] for external and [91°(–89°) and 52°] for internal. In the two cases, the substituents have opposite directions of distortions. The meso-substituted porphyrins have a high limit of twisting than usubstituted one, depending of the weight of substituents. The average of the bond angular deformations is 168°, almost planar. However, the limit of angular deformation is 94°.展开更多
Transition metal complexes of meso-tetra(4-myristyloxyphenyl)porphyrin TMPPM [M =Mn, Fe, Co, Ni, Cu, Zn; TMPP=mesotetra(4-myristyloxyphenyl)porphyrin] have been synthesized and characterized by means of elemental an...Transition metal complexes of meso-tetra(4-myristyloxyphenyl)porphyrin TMPPM [M =Mn, Fe, Co, Ni, Cu, Zn; TMPP=mesotetra(4-myristyloxyphenyl)porphyrin] have been synthesized and characterized by means of elemental analyses, UV-Vis spectra, infrared photoacoustic spectra, 1H NMR spectra, molar conductance and differential scanning calorimetry(DSC). The ligand and the Zn complex show liquid crystalline behavior. According to the DSC thermogram of the Zn complex, it exhibits a lower phase transition temperature -7.453 ℃ and a wide mesophase temperature span, 77 ℃.展开更多
The properties of porphyrins can be changed through the choice of peripheral substituents and inserted metal ions. To obtain porphyrin complexes with novel structures, 5,10, 15,20-tetrakis（p-4-fluorobenzoyloxy） phen...The properties of porphyrins can be changed through the choice of peripheral substituents and inserted metal ions. To obtain porphyrin complexes with novel structures, 5,10, 15,20-tetrakis（p-4-fluorobenzoyloxy） phenyl perphyrin（TFBOPPH2 ） and its transition metal complexes {TFBOPPM [ M = Mn（ Ⅲ ）, Fe（ Ⅲ ）, Co（ Ⅱ ）, Ni（ Ⅱ ）, Cu（ Ⅱ ） and Zn（ Ⅱ ） ] } were synthesized and characterized by means of UV-Vis, IR photoacoustic speetrumetry, ^1H NMR, elemental analyses, molar conductance, and XPS methods. A structure is proposed, in which one porphyrln molecule is coordinated with a transition metal ion in a tetradentate fashion, while the chlorine ion is the balaneeable anion in Fe（ Ⅲ ） and Mn（ Ⅲ ） complexes.展开更多
MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the ...MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the relatively stable aggregates contain equal numbers of MTBPyP4(+) and SiW12O404-.展开更多
Developing cheap and efficient electrocatalysts for water splitting is required for energy conversion techniques.Many first-row transition metal complexes have been shown to be active for the hydrogen evolution reacti...Developing cheap and efficient electrocatalysts for water splitting is required for energy conversion techniques.Many first-row transition metal complexes have been shown to be active for the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).Metal ions play crucial roles in these catalytic processes,but the activity dependence on the nature of metal ions has been rarely studied due to the difficulty to compare metal complexes with different coordination environments.We herein reported the synthesis of a series of metal complexes of azido-substituted porphyrin(1),in which metal ions have very similar coordination environments.By grafting 1-M(M=Mn,Fe,Co,Ni,and Cu)onto alkynefunctionalized carbon nanotubes(CNTs)through the same covalent connection,the resulted hybrids 1-M@CNT were all active and robust for both electrocatalytic HER and OER in alkaline aqueous solutions.Among these hybrids,1-Fe@CNT displayed the highest electrocatalytic activity for HER,while 1-Co@CNT was the most active one for OER.Moreover,a two-electrode water electrolysis cell assembled with 1-Fe@CNT as the cathode and 1-Co@CNT as the anode required smaller applied bias potential by210 mV to get 10 mA/cm^(2)current density as compared to that assembled with Pt/C and Ir/C with the same amount of metal loading.This work is significant to correlate HER and OER activity with the nature of first-row transition metal ions and to highlight promising potential applications of molecular electrocatalysis in water splitting.展开更多
The reactions of 5- (p-hydroxyphenyl)-10, 15, 20-tris (p-methoxyphenyl) porphyrin(H2Por) 1 respectively with triruthenium dodecacarbonyl [Ru3 (CO)12] and triosmiumdodecacarbonyl [Os3 (CO)12] under N2 gave complexes 2 ...The reactions of 5- (p-hydroxyphenyl)-10, 15, 20-tris (p-methoxyphenyl) porphyrin(H2Por) 1 respectively with triruthenium dodecacarbonyl [Ru3 (CO)12] and triosmiumdodecacarbonyl [Os3 (CO)12] under N2 gave complexes 2 and 3. Treatment of 2 (and 3) withMerrifield' peptide resin gave 4 (and 5) respectively.展开更多
基金supported by Natural Science Fund of Jiangsu Province (BK20141247, BK20140447)Exceptional Talent Project in Jiangsu Province (2015-XCL-035)+3 种基金University Science Research Project of Jiangsu Province (13KJB430005, 11KJA430008)funded by the Priority Academic Program development of Jiangsu Higher Education InstitutionsJiangsu Province universities' "blue and green blue project"financial support from the ARC (CE140100012, FT130100380, and DP170102267)
文摘In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin-MtTMPyP(Mt= Cobalt(Ⅱ), Manganese(Ⅲ), or Iron(Ⅲ); TMPyP = 5, 10, 15, 20-tetrakis(N-methylpyridinium-4-yl) porphyrin) intercalated into the layer of graphene oxide(GO) by the cooperative effects of electrostatic and π-π stacking interaction between positively charged metal porphyrin and negatively charged GO sheets. Followed by reduction with hydrazine vapor, a series of novel 2 D MtTMPyP/rGO_n were fabricated. The as-prepared 2 D hybrids were fully characterized and tested as non-noble metal catalysts for oxygen reduction reaction(ORR) in an alkaline medium. The MtTMPyP/rGO_n hybrids, especially CoTMPyP/rGO_5, demonstrated an improved electrocatalytic activity for ORR and a number of exchanged electrons close to 4-electron reaction, increased stability and excellent tolerance to methanol, showing a potential alternative catalyst for ORR in fuel cells and air batteries.
文摘The reaction of 5, 10, 15, 20-tetra-(4-pyridyl) porphyrin 1 with triruthenium dodecacarbonyl [Ru3(CO)12], zinc(II) acetate, copper(II) acetate, cobalt(II) acetate afforded complexes 2a?2d respectively. Treatment of 2a?2d with Merrifield’s peptide resin obtained 3a?3d. The compounds 3a?3d reacted with methyl iodide respectively gave 4a?4d. New complexes 4a?4d have been identified by IR, UV-visible spectra, and AES.
文摘The reaction of pyrrole with 4-hydroxybenzaldehyde and 4-pyridinecarboxaldehyde afforded new porphyrin ligand 1. Treatment of 1 with copper( II ) acetate, cobalt ( II ) acetate gave complexes 2-3 respectively. 2 and 3 reacted with Merrifield's peptide resin produced 4 and 5. Complexes 4 and 5 reacted with methyl iodide respectively gave 6-7. The new compounds 1-7 have been identified by H-1 NMR, IR, MS and UV-visible spectra, elemental analysis and AES.
文摘6-Deoxy- 6-iodo-β-cyclodextrin (1) reacted with 5-(p-aminophenyl)-10, 15,20-triphenyl porphyrin(2), 5-(p-aminophenyl)-10,15,20-triphenyl nickel(Ⅱ) porphyrin [NiⅡTPPNH2P](3),5-(p-aminophenyl)-10,15,20-triphenyl manganese(Ⅲ) porphyrin [MnⅢTPPNH2P] (4) and 5-(p-aminophenyl)-10,l5,20-triphenyl carbonyl ruthenium porphyrin [RuⅡ (CO)TPPNH2P] (5) to generate the compounds 6-9, respectively. Those new compound 5-9 have been identified by 1H NMR, IR, MS and UV-visible spectra and elemental analysis.
文摘The complexes of biogenic metals (Zn2+,Cu2+,Co2+,Mn3+,Fe3+) based on meso-tetra(3,5-diisobor- nyl-4-hydroxyphenyl)porphyrin 1 were synthesized. The electrochemical behavior of these com-pounds was studied using cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. The antioxidant activity of complexes was estimated by means of the electrochemical assay based on the hydrogen atom transfer reaction to the stable radical 2,2’-diphenyl-1-picrylhydrazyl (DPPH). The RDE method was applied for this process monitoring. It was shown that the efficiency of the metal complexes (Cu2+,Co2+,Mn2+,Ni2+,Fe3+) is practically the same order as that of free base porphyrin 1. However the Zn2+ complex demonstrates significantly higher antioxidant activity, and the stoichiometry of the reaction was determined as σ = 4. The results demonstrate that porphyrin macrocycle can directly affect the antioxidant properties of 2,6-diisobornylphenol.
文摘Reactions of 5-(p-aminophenyl)-10, 15, 20-triphenyl porphyrin (1) withRu_3(CO)_(12) or M(OCOCH_3)_2 (M= Ni, Mn) afforded metalloporphyrins (4―6), respectively.6-Deoxy-6-io-do-β-cyclodextrin (2) and mono (6-O-trifluoromethanesulfonyl) pennethylatedβ-cyclodextrin (3) reacted with complexes 4―6 to give β-cyclodextrin bonded metal porphyrins(7―9) and permethylated β-cyclodextrin bonded me-tal porphyrins (10―12) respectively. These newcomplexes were identified by MS, IR, UV-visible and ~1H NMR spectra, and elemental analysis.
文摘The metal contents of Nigerian coal minerals were analyzed using an atomic absorption spectrophotometer. Calcium, Na, and Fe occurred as the major elements with concentrations ranging from 9 782 μg/g for Ca to 432 μg/g for Na whereas K, Mg, Mn, Ni, Cr, Zn, Pb, and Cu, which occurred at trace levels ranged from 673.73 μg/g for Mg to 2.97 μg/g for Mn. The results of the quantitative analysis of porphyrins extracted from the coal minerals showed that Onyeama coal has the highest amount of porphyrins (ca～0.96 μg/g) while Okpara has the lowest (ca～0.30 μg/g). The porphyrins were qualitatively characterized by a combination of thin layer chromatography (TLC), infrared, and ultraviolet-visible spectrophotometers. The results of the mid infrared analysis (MIR) showed the presence of absorption bands at 3 440 cm～1～3 450 cm-1 and 1 640 cm-1～1 680 cm-1 , which are owing to the stretching vibrations of N ─ H and C─ C of aromatics, with C─ H out of plane (oop) bending vibrations at wavenumbers less than 900 cm-1, all of which are characteristic absorptions of porphyrin free base. The ultraviolet-visible data showed prominent peaks at ～400 nm(Soret band) and at wavelength ranges of 535 nm～550 nm(β-band) and 565 nm～ 600 nm (α-band) for the coal porphyrins analyzed. The geochemical significance of the metals and porphyrins in coal minerals are discussed.
文摘A convenient synthetic method of metal dendritic porphyrins through the convergent synthetic strategy is described. The porphyrin core were linked with the synthetic fragments by forming ether or ester bonds to give five target compounds were prepared.
基金supported by the National Natural Science Foundation of China(Nos.21601025,21677029,21571025)Dalian Young Science and Technology Star Project(2017RQ156)
文摘Though the photo-physical properties of free base porphyrin are attractive, there are still problems for the materials with weak and narrow range absorption of visible light. The unsymmetrical neo-confused porphyrin derivatives were introduced as novel materials for the improvement of photo-chemical and photo-physical properties. The density function theory（DFT）and time dependent density function theory（TDDFT） were applied to calculate the absorption spectrum of unsymmetrical neo-confused porphyrin（N-CP） and metal-coordinated N-CP in various solutions. The Ni and Zn coordinated neo-confused porphyrin dipole moment values are smaller than the values of prototype porphyrin（Pro P） and N–CP. According to the electrophilicity index ω, Ni coordinated N–CP（Ni–N–CP） is susceptible to the polarity of solvents, while the Zn coordinated derivative（Zn–N–CP） is more immune to the solvent environment. Unlike the Gouterman＇s four frontier orbital model of common porphyrin materials, the electron transitions of N–CPs and metalcoordinated N–CPs from H–2 or lower molecular orbitals also contribute to ultraviolet and visible absorption. Most of oscillator strength f values of Zn–N–CP are significantly higher than the values of Ni–N–CP, which reflects the higher absorption intensity of Q and Soret bands. The maximum wavelength at 702.2 nm in vacuum drew our attention to the novel material. The broad absorption range, intense red-shifted Q band and higher stability in solvents suggest that N–CPs, especially Zn–N–CP, can be one class of new candidate dye-sensitized materials.
文摘Experimental crystallographic structural parameters of a range of metaled meso-substituted and unsubstituted porphyrins were reviewed to show how far the meso-substitution by any functional group and the insertion of metal in the porphyrins core macrocycle may affect the geometry. The analysis of twists and angles has shown two kinds of distortions: external [T(C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-X<sup>n</sup>) and T(C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-C<sup>α</sup>)] and internal [T(N<sup>m</sup>-C<sup>α</sup>-C<sup>meso</sup>-X<sup>n</sup>) and T(N<sup>n</sup>-C<sup>α</sup>-C<sup>meso</sup>-C<sup>α</sup>)] with averages of [+6°and –6°] and [–5°and +5°], respectively. In the meso-substituted case, the external and internal twists C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-X and N-C<sup>α</sup>-C<sup>meso</sup>-X, respectively are oppositely orientated. Similar effect is observed in meso-unsubstituted of C<sup>β</sup>-C<sup>α</sup>- C<sup>meso</sup>-H and N-C<sup>α</sup>-C<sup>meso</sup>-H. However, the external distortions are more significant than internal. Considering the same order, the limit of distortions is [97°and 132°(–48°)] for external and [91°(–89°) and 52°] for internal. In the two cases, the substituents have opposite directions of distortions. The meso-substituted porphyrins have a high limit of twisting than usubstituted one, depending of the weight of substituents. The average of the bond angular deformations is 168°, almost planar. However, the limit of angular deformation is 94°.
文摘Transition metal complexes of meso-tetra(4-myristyloxyphenyl)porphyrin TMPPM [M =Mn, Fe, Co, Ni, Cu, Zn; TMPP=mesotetra(4-myristyloxyphenyl)porphyrin] have been synthesized and characterized by means of elemental analyses, UV-Vis spectra, infrared photoacoustic spectra, 1H NMR spectra, molar conductance and differential scanning calorimetry(DSC). The ligand and the Zn complex show liquid crystalline behavior. According to the DSC thermogram of the Zn complex, it exhibits a lower phase transition temperature -7.453 ℃ and a wide mesophase temperature span, 77 ℃.
文摘The properties of porphyrins can be changed through the choice of peripheral substituents and inserted metal ions. To obtain porphyrin complexes with novel structures, 5,10, 15,20-tetrakis（p-4-fluorobenzoyloxy） phenyl perphyrin（TFBOPPH2 ） and its transition metal complexes {TFBOPPM [ M = Mn（ Ⅲ ）, Fe（ Ⅲ ）, Co（ Ⅱ ）, Ni（ Ⅱ ）, Cu（ Ⅱ ） and Zn（ Ⅱ ） ] } were synthesized and characterized by means of UV-Vis, IR photoacoustic speetrumetry, ^1H NMR, elemental analyses, molar conductance, and XPS methods. A structure is proposed, in which one porphyrln molecule is coordinated with a transition metal ion in a tetradentate fashion, while the chlorine ion is the balaneeable anion in Fe（ Ⅲ ） and Mn（ Ⅲ ） complexes.
基金This work was supported by the National NatUral Science Foundation of China under grant! No.29733090 and No. 29803003 the Re
文摘MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the relatively stable aggregates contain equal numbers of MTBPyP4(+) and SiW12O404-.
基金support from the Fok Ying-Tong Education Foundation for Outstanding Young Teachers in Universitythe National Natural Science Foundation of China(21773146)+1 种基金the Fundamental Research Funds for the Central Universitiesthe Research Funds of Shaanxi Normal University。
文摘Developing cheap and efficient electrocatalysts for water splitting is required for energy conversion techniques.Many first-row transition metal complexes have been shown to be active for the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).Metal ions play crucial roles in these catalytic processes,but the activity dependence on the nature of metal ions has been rarely studied due to the difficulty to compare metal complexes with different coordination environments.We herein reported the synthesis of a series of metal complexes of azido-substituted porphyrin(1),in which metal ions have very similar coordination environments.By grafting 1-M(M=Mn,Fe,Co,Ni,and Cu)onto alkynefunctionalized carbon nanotubes(CNTs)through the same covalent connection,the resulted hybrids 1-M@CNT were all active and robust for both electrocatalytic HER and OER in alkaline aqueous solutions.Among these hybrids,1-Fe@CNT displayed the highest electrocatalytic activity for HER,while 1-Co@CNT was the most active one for OER.Moreover,a two-electrode water electrolysis cell assembled with 1-Fe@CNT as the cathode and 1-Co@CNT as the anode required smaller applied bias potential by210 mV to get 10 mA/cm^(2)current density as compared to that assembled with Pt/C and Ir/C with the same amount of metal loading.This work is significant to correlate HER and OER activity with the nature of first-row transition metal ions and to highlight promising potential applications of molecular electrocatalysis in water splitting.
文摘The reactions of 5- (p-hydroxyphenyl)-10, 15, 20-tris (p-methoxyphenyl) porphyrin(H2Por) 1 respectively with triruthenium dodecacarbonyl [Ru3 (CO)12] and triosmiumdodecacarbonyl [Os3 (CO)12] under N2 gave complexes 2 and 3. Treatment of 2 (and 3) withMerrifield' peptide resin gave 4 (and 5) respectively.
