Available online two new Ni_(8)Mo_(8) bimetallic coordination clusters,[Ni_(4)(TC4A)]_(2)[(Mo_5~VMo_(3)~ⅥO_(24))(PO_(4))](+Solvent)(Ni_(8)PMo_(8),H_(4)TC4A=p-tert-butylthiacalix[4]arene) and[Ni_(4)(TC4A)]_(2)[(Mo_5~V...Available online two new Ni_(8)Mo_(8) bimetallic coordination clusters,[Ni_(4)(TC4A)]_(2)[(Mo_5~VMo_(3)~ⅥO_(24))(PO_(4))](+Solvent)(Ni_(8)PMo_(8),H_(4)TC4A=p-tert-butylthiacalix[4]arene) and[Ni_(4)(TC4A)]_(2)[(Mo_5~VMo_(3)~ⅥO_(24))(OH)(CO_(3))](+Solvent)(Ni_(8)Mo_(8)),were synthesized by solvothermal method and structurally characterized by single-crystal X-ray diffraction,powder X-ray diffraction,FT-IR spectroscopy,and TGA experiments,respectively.The usage of H_(3)PMo_(12)O_(40) as source for Ni_(8)PMo_(8) resulted a sandwich like structure built from two Ni_(4)-thiacalix[4]arene units and a Mo_(8) polyoxometalate with inner spaces of PO_(4)^(3-).Ni_(8)Mo_(8) with the similar structure to that of Ni_(8)PMo_(8) is from H_(2)MoO_(4) starting reagent with OH^(-)and CO_(3)^(2-)anions encapsulated in the center.The two clusters can be directly loaded on carbon paper and utilized as working electrodes which showed distinguishable performances for glucose detection and oxidation.This work provides a better understanding of the structure-property relationships in using substituted polyoxometalates for electrochemical applications and is helpful for building calixarene-based or polyoxometalatebased functional materials.展开更多
Comprehensive Summary Isochromanone is the core structure of many bioactive compounds.Direct oxidation of isochromans is one of leading methods for the construction of isochromanones,while most established processes r...Comprehensive Summary Isochromanone is the core structure of many bioactive compounds.Direct oxidation of isochromans is one of leading methods for the construction of isochromanones,while most established processes remain suffering from the use of environmentally unfriendly metal oxidants,harsh reaction conditions,and the difficulty in catalyst recycling and product separation.Herein,we report a convenient,cost-effective,and green method for the synthesis of high-value added isochromanones via isochroman oxidations with O_(2) by a novel heterogeneous vanadium cluster catalyst(Cat.1)under mild conditions.This reaction protocol demonstrates high catalytic activity with good catalyst recyclability and reusability for a wide scope of substrates.展开更多
The gadolinium extraction by the mixtures of p-phosphorylated calixarene and 1-phenyl-3-methyl-4-benzoylpyrazalone-5 from nitrate medium was studied,which indicated an obvious synergistic effect between these two extr...The gadolinium extraction by the mixtures of p-phosphorylated calixarene and 1-phenyl-3-methyl-4-benzoylpyrazalone-5 from nitrate medium was studied,which indicated an obvious synergistic effect between these two extractants.The extractants exhibit no interaction with each other before the metal extraction.Gadolinium(Ⅲ)was extracted by the species of Ln(PMBP)_(2)L_(2)(NO_(3))instead of Ln(PMBP)_(3)•(HPMBP)or Ln(NO_(3))_(3)•2L which are extracted by HPMBP or L alone.Thermodynamic functions(ΔG,ΔH,ΔS)were calculated.The extraction of other rare earths was also investigated and compared.Possible single rare earth separation was discussed.展开更多
基金supported by the National Natural Science Foundation of China(No.91961110)。
文摘Available online two new Ni_(8)Mo_(8) bimetallic coordination clusters,[Ni_(4)(TC4A)]_(2)[(Mo_5~VMo_(3)~ⅥO_(24))(PO_(4))](+Solvent)(Ni_(8)PMo_(8),H_(4)TC4A=p-tert-butylthiacalix[4]arene) and[Ni_(4)(TC4A)]_(2)[(Mo_5~VMo_(3)~ⅥO_(24))(OH)(CO_(3))](+Solvent)(Ni_(8)Mo_(8)),were synthesized by solvothermal method and structurally characterized by single-crystal X-ray diffraction,powder X-ray diffraction,FT-IR spectroscopy,and TGA experiments,respectively.The usage of H_(3)PMo_(12)O_(40) as source for Ni_(8)PMo_(8) resulted a sandwich like structure built from two Ni_(4)-thiacalix[4]arene units and a Mo_(8) polyoxometalate with inner spaces of PO_(4)^(3-).Ni_(8)Mo_(8) with the similar structure to that of Ni_(8)PMo_(8) is from H_(2)MoO_(4) starting reagent with OH^(-)and CO_(3)^(2-)anions encapsulated in the center.The two clusters can be directly loaded on carbon paper and utilized as working electrodes which showed distinguishable performances for glucose detection and oxidation.This work provides a better understanding of the structure-property relationships in using substituted polyoxometalates for electrochemical applications and is helpful for building calixarene-based or polyoxometalatebased functional materials.
基金the National Natural Science Foundation of China(22171122)the Liaoning Revitalization Talents Program(XLYC2007130)Talent Scientific Research Fund of Liaoning Petrochemical University(2016XJL-019).
文摘Comprehensive Summary Isochromanone is the core structure of many bioactive compounds.Direct oxidation of isochromans is one of leading methods for the construction of isochromanones,while most established processes remain suffering from the use of environmentally unfriendly metal oxidants,harsh reaction conditions,and the difficulty in catalyst recycling and product separation.Herein,we report a convenient,cost-effective,and green method for the synthesis of high-value added isochromanones via isochroman oxidations with O_(2) by a novel heterogeneous vanadium cluster catalyst(Cat.1)under mild conditions.This reaction protocol demonstrates high catalytic activity with good catalyst recyclability and reusability for a wide scope of substrates.
基金This work was supported by 973 Program(No.2012CBA01206)the National Natural Science Foundation of China(Nos.21221061,21301170 and 51222404).
文摘The gadolinium extraction by the mixtures of p-phosphorylated calixarene and 1-phenyl-3-methyl-4-benzoylpyrazalone-5 from nitrate medium was studied,which indicated an obvious synergistic effect between these two extractants.The extractants exhibit no interaction with each other before the metal extraction.Gadolinium(Ⅲ)was extracted by the species of Ln(PMBP)_(2)L_(2)(NO_(3))instead of Ln(PMBP)_(3)•(HPMBP)or Ln(NO_(3))_(3)•2L which are extracted by HPMBP or L alone.Thermodynamic functions(ΔG,ΔH,ΔS)were calculated.The extraction of other rare earths was also investigated and compared.Possible single rare earth separation was discussed.
