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
Photovoltage properties and charge transfer process of tailed porpbyrin Mn(Ⅲ) complex. meso-mono-|o-(4-diethylamino) butyramidophenyl| triphenyl porphyrin Mn(Ⅲ) (MDBPTPPMn(Ⅲ)Cl) were investigated by surface photovo...Photovoltage properties and charge transfer process of tailed porpbyrin Mn(Ⅲ) complex. meso-mono-|o-(4-diethylamino) butyramidophenyl| triphenyl porphyrin Mn(Ⅲ) (MDBPTPPMn(Ⅲ)Cl) were investigated by surface photovoltage spectrum (SPS)and field modulation surface photovoltage spectrum (FMSPS). Furthermore, its absorption spectra in near-ultraviolet and near-infrared that have been disputed are given a new assignment in this paper.展开更多
The treatment of tetrakis (4-pyridyl) porphyrin H2TPyP with a hydrated rare earth (III) acetylacetonate RE(acac)3 · nH2O (RE=Y, Eu, Gd) in 1,2, 4-trichlorobenzene (TCB) pro- duced a monomeric porphyrinato rare e...The treatment of tetrakis (4-pyridyl) porphyrin H2TPyP with a hydrated rare earth (III) acetylacetonate RE(acac)3 · nH2O (RE=Y, Eu, Gd) in 1,2, 4-trichlorobenzene (TCB) pro- duced a monomeric porphyrinato rare earth compound RE (TPyP) acac, which further reacted with dicyanobenzene in amyl alcohol in the presence of 1, 8-diazabicyclo [5. 4. 0] undec-7-ene (DBU), giving HRE(TPyP) (Pc) in a good yield. Upon exposure to air, part of the protonated mixed double-deckers in CHC13 solutions converted slowly to the corresponding neutral complexes RE (TPyP) (Pc). These protonated complexes were characterized by means of UV-V is, IR, NMR, mass spectroscopies. The quaternarization of these protonated mixed double-deckers with methyl iodide produced the salts of tetramethylated cations [HRE(TMPyP) (Pc)]4+.展开更多
The method of Adler was improved to prepare a series of 5,10,15,20-tetrakis(4-alkoxyphenyl)porphyrins and their complexes containing Fe3+, Mn3+, Pb2+, Co2+, Cu2+, Zn2+. Among them there were seven new compounds. All t...The method of Adler was improved to prepare a series of 5,10,15,20-tetrakis(4-alkoxyphenyl)porphyrins and their complexes containing Fe3+, Mn3+, Pb2+, Co2+, Cu2+, Zn2+. Among them there were seven new compounds. All these compounds were identified through 1H NMR, MS, IR, UV and Element analysis. The correlation between the structure of compounds and their 1H NMR, MS, IR, UV spectra was discussed and their specific spectra were explained. We found nine metalloporphyrins exhibited liquid crystal behaviour through DSC and polarized-light microscope. They had one to three mesophases and certain phase transition temperature, ?H and temperature range of L.C(?T).展开更多
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-.
文摘Photovoltage properties and charge transfer process of tailed porpbyrin Mn(Ⅲ) complex. meso-mono-|o-(4-diethylamino) butyramidophenyl| triphenyl porphyrin Mn(Ⅲ) (MDBPTPPMn(Ⅲ)Cl) were investigated by surface photovoltage spectrum (SPS)and field modulation surface photovoltage spectrum (FMSPS). Furthermore, its absorption spectra in near-ultraviolet and near-infrared that have been disputed are given a new assignment in this paper.
基金Educational Ministry of China, Natural Science Foundation of China (Grant No. 29701002, 29992590-4), the Visiting Scholar Foun
文摘The treatment of tetrakis (4-pyridyl) porphyrin H2TPyP with a hydrated rare earth (III) acetylacetonate RE(acac)3 · nH2O (RE=Y, Eu, Gd) in 1,2, 4-trichlorobenzene (TCB) pro- duced a monomeric porphyrinato rare earth compound RE (TPyP) acac, which further reacted with dicyanobenzene in amyl alcohol in the presence of 1, 8-diazabicyclo [5. 4. 0] undec-7-ene (DBU), giving HRE(TPyP) (Pc) in a good yield. Upon exposure to air, part of the protonated mixed double-deckers in CHC13 solutions converted slowly to the corresponding neutral complexes RE (TPyP) (Pc). These protonated complexes were characterized by means of UV-V is, IR, NMR, mass spectroscopies. The quaternarization of these protonated mixed double-deckers with methyl iodide produced the salts of tetramethylated cations [HRE(TMPyP) (Pc)]4+.
文摘The method of Adler was improved to prepare a series of 5,10,15,20-tetrakis(4-alkoxyphenyl)porphyrins and their complexes containing Fe3+, Mn3+, Pb2+, Co2+, Cu2+, Zn2+. Among them there were seven new compounds. All these compounds were identified through 1H NMR, MS, IR, UV and Element analysis. The correlation between the structure of compounds and their 1H NMR, MS, IR, UV spectra was discussed and their specific spectra were explained. We found nine metalloporphyrins exhibited liquid crystal behaviour through DSC and polarized-light microscope. They had one to three mesophases and certain phase transition temperature, ?H and temperature range of L.C(?T).
