The anion coordination complex,[ClPt(bpt)4]Cl (bpt=N,N'-bis(3-pyridylmethyl)-2-thiourea),was synthesized and studied by X-ray crystal structure analysis,NMR and FAB mass spectra. In the solid state,the Pt(bpt)4 ...The anion coordination complex,[ClPt(bpt)4]Cl (bpt=N,N'-bis(3-pyridylmethyl)-2-thiourea),was synthesized and studied by X-ray crystal structure analysis,NMR and FAB mass spectra. In the solid state,the Pt(bpt)4 anion receptor adopts a cone conformation to bind the chloride anion through hydrogen bonds and electrostatic interaction in which the four branches of the thiourea ligands bind the chloride anion to form N-H…Cl-hydrogen bonds (3.49-3.81). The entraped chloride anion is situated above the Pt(Ⅱ) center at 3.52 . Further second-sphere coordination assemby from the Pt(bpt)4 core with 8 zinc(Ⅱ) tetraphenylporphyrins (ZnPr) is discussed.展开更多
The stability constants of some ternary mixed-ligand complexes, Pt(Phen)(CA)+, where Phen=1,10-phenanthroline and CA- =carboxylate, were determined by means of potentiometric pH titration in aqueous solutions(I=0.1 mo...The stability constants of some ternary mixed-ligand complexes, Pt(Phen)(CA)+, where Phen=1,10-phenanthroline and CA- =carboxylate, were determined by means of potentiometric pH titration in aqueous solutions(I=0.1 mol/L, KNO 3; 25 ℃), and the stability of them was compared with that of the corresponding binary complexes. It was revealed that the ternary complexes containing phenylalkane carboxylates ligands(PCA-) are much more stable than those formed with formate and acetate. The results indicate that there exist the intramolecular aromatic-ring interactions between the phenanthroline ring of Phen and the phenyl moiety of ligand PCA- in the ternary mixed-ligand Pt(Phen)(PCA)- complexes. The extent of the stacking interactions, which depends on the number of methylene groups between the phenyl moieties and the coordinated phenylalkane carboxylate groups, was calculated. The best-fitted stack was obtained for the complexes with 2-phenylacetate and 3-phenylpropionate as the ligands.展开更多
With visible light(λ=450 nm) irradiation of a catalytic amount of platinum(Ⅱ) terpyridyl complex, 1,3,5-triaryl-2-pyrazolines can be smoothly converted to their corresponding pyrazoles and hydrogen in quantitative y...With visible light(λ=450 nm) irradiation of a catalytic amount of platinum(Ⅱ) terpyridyl complex, 1,3,5-triaryl-2-pyrazolines can be smoothly converted to their corresponding pyrazoles and hydrogen in quantitative yields with no use of any oxidant at room temperature.展开更多
The stability constants of the ternary mixed ligand complexes Pt(Phen)(CA) +(Phen=1,10 Phenanathroline,CA=carboxylate Ligands) were determined by potentiometric pH titration in aqueous solution and in 30～90%(V/V) aqu...The stability constants of the ternary mixed ligand complexes Pt(Phen)(CA) +(Phen=1,10 Phenanathroline,CA=carboxylate Ligands) were determined by potentiometric pH titration in aqueous solution and in 30～90%(V/V) aqueous ethanal(I=0.1mol·L -1 ,KNO 3;25℃).The difference of stability among the different complexes was compared and discussed,and the percentages of the stacked isomers in the ternary mixed ligand complexes Pt(Phen)(PCA) +(PCA=2 phenylacetate and 3 phenylpropionate) was calculated.The experimental results indicate that the extent of the intramolecular aromatic ring stacking interaction in the ternary mixed ligand Pt(Phen)(PCA) + complexes depends on the polarity of the solution.The weaker the polarity of the solution,the more notable the intramolecular aromatic ring stacking interaction,the larger the percentage of the stacked isomers in the ternary complexes,and the more stable the ternary mixed ligand complexes.展开更多
Understanding the impact of substituents on the quantum interference effect at single molecule scale is of great importance for the design of molecular devices.In this work,three platinum(Ⅱ)complexes with–H,–NH_(2)...Understanding the impact of substituents on the quantum interference effect at single molecule scale is of great importance for the design of molecular devices.In this work,three platinum(Ⅱ)complexes with–H,–NH_(2)and–NO_(2)groups on conductive backbones were designed and synthesized.Single-molecule conductance,which was measured using scanning tunnelling microscope break junction(STM-BJ)technique,demonstrated a conductance freeze phenomenon under the variation of substituents.Theoretical study revealed that,despite the electronic effect of the substituents shifting the energy level of molecular orbital,the quantum interference effect vanished the influence of electronic effect on the conductance and eventually leaded to the conductance freeze.展开更多
基金supported by the National Natural Science Foundation of China(21073143)“Chunhui Project”from the Ministry of Education of China(Z2009-1-71002,Z2009-1-71006)+2 种基金Graduate Starting Seed Fund of Northwestern Polytechnical University(NPU),China(Z2015152)NPU Foundation for Graduate InnovationChina~~
基金Supported by the National Natural Science Foundation of China (Grant Nos. 50673098 & 20772152)Renmin University of China, State Key Laboratory of Structure Chemistry (Grant No. 20080052)
文摘The anion coordination complex,[ClPt(bpt)4]Cl (bpt=N,N'-bis(3-pyridylmethyl)-2-thiourea),was synthesized and studied by X-ray crystal structure analysis,NMR and FAB mass spectra. In the solid state,the Pt(bpt)4 anion receptor adopts a cone conformation to bind the chloride anion through hydrogen bonds and electrostatic interaction in which the four branches of the thiourea ligands bind the chloride anion to form N-H…Cl-hydrogen bonds (3.49-3.81). The entraped chloride anion is situated above the Pt(Ⅱ) center at 3.52 . Further second-sphere coordination assemby from the Pt(bpt)4 core with 8 zinc(Ⅱ) tetraphenylporphyrins (ZnPr) is discussed.
基金Supported by the Foundation of Academ y L eader of Zhejiang Gongshang U niversity(No.19972 0 0 2 )
文摘The stability constants of some ternary mixed-ligand complexes, Pt(Phen)(CA)+, where Phen=1,10-phenanthroline and CA- =carboxylate, were determined by means of potentiometric pH titration in aqueous solutions(I=0.1 mol/L, KNO 3; 25 ℃), and the stability of them was compared with that of the corresponding binary complexes. It was revealed that the ternary complexes containing phenylalkane carboxylates ligands(PCA-) are much more stable than those formed with formate and acetate. The results indicate that there exist the intramolecular aromatic-ring interactions between the phenanthroline ring of Phen and the phenyl moiety of ligand PCA- in the ternary mixed-ligand Pt(Phen)(PCA)- complexes. The extent of the stacking interactions, which depends on the number of methylene groups between the phenyl moieties and the coordinated phenylalkane carboxylate groups, was calculated. The best-fitted stack was obtained for the complexes with 2-phenylacetate and 3-phenylpropionate as the ligands.
基金supported by the National Basic Research Program of China(2013CB8345052013CB834804)+3 种基金the National Natural Science Foundation of China(213904049142730321402217)the Key Research Programme of the Chinese Academy of Sciences(KGZD-EW-T05)
文摘With visible light(λ=450 nm) irradiation of a catalytic amount of platinum(Ⅱ) terpyridyl complex, 1,3,5-triaryl-2-pyrazolines can be smoothly converted to their corresponding pyrazoles and hydrogen in quantitative yields with no use of any oxidant at room temperature.
文摘The stability constants of the ternary mixed ligand complexes Pt(Phen)(CA) +(Phen=1,10 Phenanathroline,CA=carboxylate Ligands) were determined by potentiometric pH titration in aqueous solution and in 30～90%(V/V) aqueous ethanal(I=0.1mol·L -1 ,KNO 3;25℃).The difference of stability among the different complexes was compared and discussed,and the percentages of the stacked isomers in the ternary mixed ligand complexes Pt(Phen)(PCA) +(PCA=2 phenylacetate and 3 phenylpropionate) was calculated.The experimental results indicate that the extent of the intramolecular aromatic ring stacking interaction in the ternary mixed ligand Pt(Phen)(PCA) + complexes depends on the polarity of the solution.The weaker the polarity of the solution,the more notable the intramolecular aromatic ring stacking interaction,the larger the percentage of the stacked isomers in the ternary complexes,and the more stable the ternary mixed ligand complexes.
基金the National Natural Science Foundation of China(No.92061117)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB20000000)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(No.2021ZR129)。
文摘Understanding the impact of substituents on the quantum interference effect at single molecule scale is of great importance for the design of molecular devices.In this work,three platinum(Ⅱ)complexes with–H,–NH_(2)and–NO_(2)groups on conductive backbones were designed and synthesized.Single-molecule conductance,which was measured using scanning tunnelling microscope break junction(STM-BJ)technique,demonstrated a conductance freeze phenomenon under the variation of substituents.Theoretical study revealed that,despite the electronic effect of the substituents shifting the energy level of molecular orbital,the quantum interference effect vanished the influence of electronic effect on the conductance and eventually leaded to the conductance freeze.
