Two multidentate ligands 2,9-di[6＇-（2″-hydroxyl-3″-methoxyphenyl）-n-2＇,5＇-diazahexyl]-1,10-phenanthroline（LA）and 2,9-di（6＇-α-phenol-n-2＇,5＇-diazahexyl）-1,10-phenanthroline（LB）were synthesized and full...Two multidentate ligands 2,9-di[6＇-（2″-hydroxyl-3″-methoxyphenyl）-n-2＇,5＇-diazahexyl]-1,10-phenanthroline（LA）and 2,9-di（6＇-α-phenol-n-2＇,5＇-diazahexyl）-1,10-phenanthroline（LB）were synthesized and fully characterized.Protonation of the ligands and the stability of the complexes of the ligands with divalent metal ions were investigated.The trinuclear metal complexes [Cu（Ⅱ）and Zn（Ⅱ）] of the ligands were studied,as catalysts,for the transphosphorylation of the RNA-model substrate 2-hydroxypropyl-p-nitrophenyl phosphate（HPNP）.The second-order rate constants of HPNP-hydrolysis catalyzed by M3L and M3LH-1 were obtained,which indicated that Zn3LBH-1 was the most efficient catalyst among them.The proposed mechanisms included the activation of the substrate via binding to the metal ions and intramolecular nucleophilic attack by the deprotonated C2-hydroxyl of HPNP.展开更多
The title compound, N-（1′-H-pyrrol-2′-ylcarbonyl）-5-amino-1,10-phenanthroline, was synthesized by the reaction of a-pyrrolyl carbonyl chloride and 5-amino-1,10-phenanthroline in pyridine. Determined by X-ray struc...The title compound, N-（1′-H-pyrrol-2′-ylcarbonyl）-5-amino-1,10-phenanthroline, was synthesized by the reaction of a-pyrrolyl carbonyl chloride and 5-amino-1,10-phenanthroline in pyridine. Determined by X-ray structure analysis, it crystallizes in triclinic system, space group P1 with the following crystallographic data： C20H21N5O3, Mr = 379.42, a = 7.8559（4）, b = 9.1681（6）, c = 14.6818（9） A, α= 73.254（10）,β= 88.938（15）, γ= 68.080（10）°, V= 934.66（10） A3, Z = 2, F（000） = 400, Dc = 1.348 g/cm^3 and p = 0.094 mm-1. The final R = 0.0680 and wR = 0.1419 for 2142 observed reflections with I 〉 2σ（/）, and R = 0.1084 and wR = 0.1643 for all reflections. Two aromatic ring planes （pyrrole and phenanthroline rings） are connected by the amide plane. Two different types of intermolecular hydrogen bonds, O-H…N and N-H…O, exist in the crystal. The title complex molecules are connected through hydrogen bonds and weak π-π stacking interactions to generate a 3-D supramolecule.展开更多
A Maleamide bridged carbazole receptor was designed and synthesized, the interactions between the receptor and anions, such as Ac-, H2PO4-, OH-, F-, Cl-, Br- and I- in DMSO were investigated by UV-Vis spectroscopy and...A Maleamide bridged carbazole receptor was designed and synthesized, the interactions between the receptor and anions, such as Ac-, H2PO4-, OH-, F-, Cl-, Br- and I- in DMSO were investigated by UV-Vis spectroscopy and 1H NMR titration. The results of UV-Vis spectral studies indicate that interactions existed between receptor and anions, which induced remarkable color changes. The 1H NMR titration indicated amide moiety of the receptor was deprontonated first when a small quantity of anions such as Ac-, H2PO4-, F- were added; however, the carbazole N―H was gradually deprontonated upon the addition of anions.展开更多
Relative absorption intensities of the Fermi resonance polyads of isolated C-H chromophore for the CHC13 molecule are calculated by one-dimensional dipole moment surface which had been obtained by the ab initio densit...Relative absorption intensities of the Fermi resonance polyads of isolated C-H chromophore for the CHC13 molecule are calculated by one-dimensional dipole moment surface which had been obtained by the ab initio density functional method B3PW91 with 6-311++G(3df,2pd)basis set,and agree very well with the experimental results.It is shown that the nonlinearity of the dipole moment surface in the vicinity of the equilibrium configuration is responsihle for the intensities anomaly,i.e.the unusual strong intensities of the second Fermi resonance polyad.展开更多
基金Supported by the National Natural Science Foundation of China(Nos.20371028and20671052).
文摘Two multidentate ligands 2,9-di[6＇-（2″-hydroxyl-3″-methoxyphenyl）-n-2＇,5＇-diazahexyl]-1,10-phenanthroline（LA）and 2,9-di（6＇-α-phenol-n-2＇,5＇-diazahexyl）-1,10-phenanthroline（LB）were synthesized and fully characterized.Protonation of the ligands and the stability of the complexes of the ligands with divalent metal ions were investigated.The trinuclear metal complexes [Cu（Ⅱ）and Zn（Ⅱ）] of the ligands were studied,as catalysts,for the transphosphorylation of the RNA-model substrate 2-hydroxypropyl-p-nitrophenyl phosphate（HPNP）.The second-order rate constants of HPNP-hydrolysis catalyzed by M3L and M3LH-1 were obtained,which indicated that Zn3LBH-1 was the most efficient catalyst among them.The proposed mechanisms included the activation of the substrate via binding to the metal ions and intramolecular nucleophilic attack by the deprotonated C2-hydroxyl of HPNP.
基金This work was supported by the National Natural Science Foundation of China (No. 20371028 and 20671052)
文摘The title compound, N-（1′-H-pyrrol-2′-ylcarbonyl）-5-amino-1,10-phenanthroline, was synthesized by the reaction of a-pyrrolyl carbonyl chloride and 5-amino-1,10-phenanthroline in pyridine. Determined by X-ray structure analysis, it crystallizes in triclinic system, space group P1 with the following crystallographic data： C20H21N5O3, Mr = 379.42, a = 7.8559（4）, b = 9.1681（6）, c = 14.6818（9） A, α= 73.254（10）,β= 88.938（15）, γ= 68.080（10）°, V= 934.66（10） A3, Z = 2, F（000） = 400, Dc = 1.348 g/cm^3 and p = 0.094 mm-1. The final R = 0.0680 and wR = 0.1419 for 2142 observed reflections with I 〉 2σ（/）, and R = 0.1084 and wR = 0.1643 for all reflections. Two aromatic ring planes （pyrrole and phenanthroline rings） are connected by the amide plane. Two different types of intermolecular hydrogen bonds, O-H…N and N-H…O, exist in the crystal. The title complex molecules are connected through hydrogen bonds and weak π-π stacking interactions to generate a 3-D supramolecule.
基金the National Natural Science Foundation of China(Nos.20391028 and 20671052)
文摘A Maleamide bridged carbazole receptor was designed and synthesized, the interactions between the receptor and anions, such as Ac-, H2PO4-, OH-, F-, Cl-, Br- and I- in DMSO were investigated by UV-Vis spectroscopy and 1H NMR titration. The results of UV-Vis spectral studies indicate that interactions existed between receptor and anions, which induced remarkable color changes. The 1H NMR titration indicated amide moiety of the receptor was deprontonated first when a small quantity of anions such as Ac-, H2PO4-, F- were added; however, the carbazole N―H was gradually deprontonated upon the addition of anions.
基金Supported by the National Natrual Science Foundation of China(No.0098GG03-71)the Chinese Academy of Sciences(No.KJ951-Al-510).
文摘Relative absorption intensities of the Fermi resonance polyads of isolated C-H chromophore for the CHC13 molecule are calculated by one-dimensional dipole moment surface which had been obtained by the ab initio density functional method B3PW91 with 6-311++G(3df,2pd)basis set,and agree very well with the experimental results.It is shown that the nonlinearity of the dipole moment surface in the vicinity of the equilibrium configuration is responsihle for the intensities anomaly,i.e.the unusual strong intensities of the second Fermi resonance polyad.
