A novel N-（2-hydroxy-5-chlorodibenzophenone）-N＇-[2-hydroxy-5-azophenyl-benzaldehyde]- 1,2-diaminobenzene receptor has been synthesized by simple steps with good yields. The anion recognition properties were studied...A novel N-（2-hydroxy-5-chlorodibenzophenone）-N＇-[2-hydroxy-5-azophenyl-benzaldehyde]- 1,2-diaminobenzene receptor has been synthesized by simple steps with good yields. The anion recognition properties were studied by ultraviolet-visible spectroscopy. The results showed that the receptor had a higher affinity to F-, AcO-, and H2PO4-, but no evident binding with Cl-, Br-, and l-. Upon addition of the three former anions to the receptors in DMSO, the solution exhibited an obvious color change from colorless to yellow, which could be observed by the naked eye, thus the receptor could act as a fluoride ion sensor even in the presence of other halide ions. The UV-Vis data indicates that a 1：1 stoichiometric complex is formed through hydrogen bonding interactions between receptor and anions.展开更多
A single-Rh-site catalyst(Rh-TPISP)that was ionically-embedded on a P(V)quaternary phosphonium porous polymer was evaluated for heterogeneous ethanol carbonylation.The[Rh(CO)I_(3)]^(2-)unit was proposed to be the acti...A single-Rh-site catalyst(Rh-TPISP)that was ionically-embedded on a P(V)quaternary phosphonium porous polymer was evaluated for heterogeneous ethanol carbonylation.The[Rh(CO)I_(3)]^(2-)unit was proposed to be the active center of Rh-TPISP for the carbonylation reaction based on detailed Rh L3-edge X-ray absorption near edge structure(XANES),X-ray photoelectron spectroscopy(XPS),and Rh extended X-ray absorption fine structure(EXAFS)analyses.As the highlight of this study,Rh-TPISP displayed distinctly higher activity for heterogeneous ethanol carbonylation than the reported catalytic systems in which[Rh(CO)_(2)I_(2)]^(-)is the traditional active center.A TOF of 350 h^(-1)was obtained for the reaction over[Rh(CO)I_(3)]^(2-),with>95%propionyl selectivity at 3.5 MPa and 468 K.No deactivation was detected during a near 1000 h running test.The more electron-rich Rh center was thought to be crucial for explaining the superior activity and selectivity of Rh-TPISP,and the formation of two ionic bonds between[Rh(CO)I_(3)]^(2-)and the cationic P(V)framework([P]^(+))of the polymer was suggested to play a key role in firmly immobilizing the active species to prevent Rh leaching.展开更多
The interactions of complexes of XeOF_(2) and XeO_(3) with a series of different hybridization N-containing donors are studied by means of DFT and MP_(2) calculations.The aerogen bonding interaction energies range fro...The interactions of complexes of XeOF_(2) and XeO_(3) with a series of different hybridization N-containing donors are studied by means of DFT and MP_(2) calculations.The aerogen bonding interaction energies range from 6.5 kcal/mol to19.9 kcal/mol between XeO_(3) or XeOF_(2) and typical N-containing donors.The sequence of interaction for N-containing hy-bridization is sp^(3)>sp^(2)>sp,and XeO_(3)is higher than XeOF_(2).For some donors of sp^(2)and sp^(3) hybridization,the steric effect plays a minor role in the interaction with the evidence of reduced density gradient plots.The dominant stable part is the electrostatic interaction.In complex of XeO_(3),the weight of polarization is larger than dispersion,while the situation is opposite for XeOF_(2)complexes.Except for the sum of the maximum value of molecular electrostatic potential on Xe atom and minimum value of molecular electrostatic potential on N atom,the other five interaction parameters including the potential energy density at bond critical point,the equilibrium distances,interaction energies with the basis set superposition error correction,localized molecular orbital energy decomposition analysis interaction energies,and the electron charge density,show great linear correlation coefficients with each other.展开更多
基金ACKNOWLEDGMENTSV. ACKNOWLEDGMENTS This work is supported by the Natural Science Foundation of Universities of Inner Mongolia Autonomous Region （No.NG09168） and the Star-up fund of Nanjing University （No.163101026）.
文摘A novel N-（2-hydroxy-5-chlorodibenzophenone）-N＇-[2-hydroxy-5-azophenyl-benzaldehyde]- 1,2-diaminobenzene receptor has been synthesized by simple steps with good yields. The anion recognition properties were studied by ultraviolet-visible spectroscopy. The results showed that the receptor had a higher affinity to F-, AcO-, and H2PO4-, but no evident binding with Cl-, Br-, and l-. Upon addition of the three former anions to the receptors in DMSO, the solution exhibited an obvious color change from colorless to yellow, which could be observed by the naked eye, thus the receptor could act as a fluoride ion sensor even in the presence of other halide ions. The UV-Vis data indicates that a 1：1 stoichiometric complex is formed through hydrogen bonding interactions between receptor and anions.
文摘A single-Rh-site catalyst(Rh-TPISP)that was ionically-embedded on a P(V)quaternary phosphonium porous polymer was evaluated for heterogeneous ethanol carbonylation.The[Rh(CO)I_(3)]^(2-)unit was proposed to be the active center of Rh-TPISP for the carbonylation reaction based on detailed Rh L3-edge X-ray absorption near edge structure(XANES),X-ray photoelectron spectroscopy(XPS),and Rh extended X-ray absorption fine structure(EXAFS)analyses.As the highlight of this study,Rh-TPISP displayed distinctly higher activity for heterogeneous ethanol carbonylation than the reported catalytic systems in which[Rh(CO)_(2)I_(2)]^(-)is the traditional active center.A TOF of 350 h^(-1)was obtained for the reaction over[Rh(CO)I_(3)]^(2-),with>95%propionyl selectivity at 3.5 MPa and 468 K.No deactivation was detected during a near 1000 h running test.The more electron-rich Rh center was thought to be crucial for explaining the superior activity and selectivity of Rh-TPISP,and the formation of two ionic bonds between[Rh(CO)I_(3)]^(2-)and the cationic P(V)framework([P]^(+))of the polymer was suggested to play a key role in firmly immobilizing the active species to prevent Rh leaching.
基金financially supported by the China Postdoctoral Science Foundation(No.2020M682154)。
文摘The interactions of complexes of XeOF_(2) and XeO_(3) with a series of different hybridization N-containing donors are studied by means of DFT and MP_(2) calculations.The aerogen bonding interaction energies range from 6.5 kcal/mol to19.9 kcal/mol between XeO_(3) or XeOF_(2) and typical N-containing donors.The sequence of interaction for N-containing hy-bridization is sp^(3)>sp^(2)>sp,and XeO_(3)is higher than XeOF_(2).For some donors of sp^(2)and sp^(3) hybridization,the steric effect plays a minor role in the interaction with the evidence of reduced density gradient plots.The dominant stable part is the electrostatic interaction.In complex of XeO_(3),the weight of polarization is larger than dispersion,while the situation is opposite for XeOF_(2)complexes.Except for the sum of the maximum value of molecular electrostatic potential on Xe atom and minimum value of molecular electrostatic potential on N atom,the other five interaction parameters including the potential energy density at bond critical point,the equilibrium distances,interaction energies with the basis set superposition error correction,localized molecular orbital energy decomposition analysis interaction energies,and the electron charge density,show great linear correlation coefficients with each other.
