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
Though there are numerous intrinsic merits of metal-organic frameworks(MOFs),low charge separation efficiency has imposed heavy restrictions on their photocatalytic application.Herein,in situ porphyrin ligand substitu...Though there are numerous intrinsic merits of metal-organic frameworks(MOFs),low charge separation efficiency has imposed heavy restrictions on their photocatalytic application.Herein,in situ porphyrin ligand substitution,as a strategy for improving the charge separation efficiency and increasing the amounts of active sites,has been designed and realized in a Hf-biphenyl dicarboxylic acid(BPDC)MOF.Specifically,a size and geometry matched meso-tetra(4-carboxyphenyl)porphyrin(TCPP)ligand was selected and doped into Hf-BPDC MOF by forming coordinating bonds with Hf centers,forming dualligand Hf-BPDC-TCPP MOF.The resultant Hf-BPDC-TCPP MOF showed significantly improved activity and chemical stability in the photocatalytic H_(2)generation(261μmol·g^(-1)·h^(-1))and tetracycline(TC)degradation reactions(95.8%),which was 48 and 1.47 folds higher than that of the Hf-BPDC MOF.Photophysical and electrochemical studies revealed that the introduction of porphyrin ligand could generate a stronger internal electric field for boosting the charge separation and transfer,increase the specific surface area for providing more active sites,and narrow the band gap to enhance the visible light absorption.This in situ ligand substitution method provides a promising approach to build a tunable platform for constructing high-performance MOF photocatalysts.展开更多
A spectrometric setup to perform total internal reflection fluorescence (TIRF) and synchronous TIRF measurements at solid/liquid interfaces is presented. The combination of TIRF and synchronous fluorescence was propo...A spectrometric setup to perform total internal reflection fluorescence (TIRF) and synchronous TIRF measurements at solid/liquid interfaces is presented. The combination of TIRF and synchronous fluorescence was proposed to analyze simultaneously different components at interfaces. The TIRF excitation, emission and synchronous spectra of a watersoluble porphyrin were obtained from water/glass interface using this setup without the existence of a surfactant.展开更多
A novel zinc porphyrin, {[ZnTCPP（EtOH）][Zn（en）]2},（EtOH）2, （1） （TCPP=meso-tetra（4-carboxyphenyl）- porphyrin; EtOH=ethanol; en=ethylenediamine） was obtained via a hydrothermal reaction and characterized by ...A novel zinc porphyrin, {[ZnTCPP（EtOH）][Zn（en）]2},（EtOH）2, （1） （TCPP=meso-tetra（4-carboxyphenyl）- porphyrin; EtOH=ethanol; en=ethylenediamine） was obtained via a hydrothermal reaction and characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the space group C2/c of the monoclinie system with eight formula units in a cell： a=32.465（4） A, b=10.527（3） A, c=31.845（3） A,β=95.524（6）°, V=10832（4） A3, C58H57NsOaIZn3, Mr= 1238.23, Dc= 1.518 g/cm3, S=1.005, μ（Mo Kα）= 1.388 mm-1, F（000）=5112, R=0.0650 and wR=0.1574. Complex 1 features a novel 2-D layered motif. The spectral data of UV-vis, FT-IR and fluorescence are reported.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 ℃.
基金financially supported by the National Nature Science Foundation of China(Nos.22102064 and 21972058)supported by the Open Project Program of Fujian Provincial Key Laboratory of Ecology-Toxicological Effects and Control for Emerging Contaminants,Putian University。
文摘Though there are numerous intrinsic merits of metal-organic frameworks(MOFs),low charge separation efficiency has imposed heavy restrictions on their photocatalytic application.Herein,in situ porphyrin ligand substitution,as a strategy for improving the charge separation efficiency and increasing the amounts of active sites,has been designed and realized in a Hf-biphenyl dicarboxylic acid(BPDC)MOF.Specifically,a size and geometry matched meso-tetra(4-carboxyphenyl)porphyrin(TCPP)ligand was selected and doped into Hf-BPDC MOF by forming coordinating bonds with Hf centers,forming dualligand Hf-BPDC-TCPP MOF.The resultant Hf-BPDC-TCPP MOF showed significantly improved activity and chemical stability in the photocatalytic H_(2)generation(261μmol·g^(-1)·h^(-1))and tetracycline(TC)degradation reactions(95.8%),which was 48 and 1.47 folds higher than that of the Hf-BPDC MOF.Photophysical and electrochemical studies revealed that the introduction of porphyrin ligand could generate a stronger internal electric field for boosting the charge separation and transfer,increase the specific surface area for providing more active sites,and narrow the band gap to enhance the visible light absorption.This in situ ligand substitution method provides a promising approach to build a tunable platform for constructing high-performance MOF photocatalysts.
文摘A spectrometric setup to perform total internal reflection fluorescence (TIRF) and synchronous TIRF measurements at solid/liquid interfaces is presented. The combination of TIRF and synchronous fluorescence was proposed to analyze simultaneously different components at interfaces. The TIRF excitation, emission and synchronous spectra of a watersoluble porphyrin were obtained from water/glass interface using this setup without the existence of a surfactant.
文摘A novel zinc porphyrin, {[ZnTCPP（EtOH）][Zn（en）]2},（EtOH）2, （1） （TCPP=meso-tetra（4-carboxyphenyl）- porphyrin; EtOH=ethanol; en=ethylenediamine） was obtained via a hydrothermal reaction and characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the space group C2/c of the monoclinie system with eight formula units in a cell： a=32.465（4） A, b=10.527（3） A, c=31.845（3） A,β=95.524（6）°, V=10832（4） A3, C58H57NsOaIZn3, Mr= 1238.23, Dc= 1.518 g/cm3, S=1.005, μ（Mo Kα）= 1.388 mm-1, F（000）=5112, R=0.0650 and wR=0.1574. Complex 1 features a novel 2-D layered motif. The spectral data of UV-vis, FT-IR and fluorescence are reported.
