Complexes of La(Ⅲ),Nd(Ⅲ),Sm(Ⅲ),Eu(Ⅲ),Gd(Ⅲ),Dy(Ⅲ), Er(Ⅲ),Yb(Ⅲ)and Y(Ⅲ)with piperonal isonicotinoyl hydrazone(HPIN) have been synthesized in DMF and EtOH.The complexes have been characte- rized by elemental ana...Complexes of La(Ⅲ),Nd(Ⅲ),Sm(Ⅲ),Eu(Ⅲ),Gd(Ⅲ),Dy(Ⅲ), Er(Ⅲ),Yb(Ⅲ)and Y(Ⅲ)with piperonal isonicotinoyl hydrazone(HPIN) have been synthesized in DMF and EtOH.The complexes have been characte- rized by elemental analysis,molar conductance,i.r.,UV and^1H n.m.r. spectra,magnetic measurements,X-ray powder diffraction and DTA.展开更多
A new method of using nanometer TiO 2 as solid phase extractant coupled with ICP AES was proposed for speciation of rare earth elements. The adsorption behavior of rare earth complexes on nanometer TiO 2 was inves...A new method of using nanometer TiO 2 as solid phase extractant coupled with ICP AES was proposed for speciation of rare earth elements. The adsorption behavior of rare earth complexes on nanometer TiO 2 was investigated. Effect of pH value, contact time, elution solution and interfering ions on the recovery of the rare earth complexes were studied. A quantitative recovery (>90%) was found in the pH range of 4~9.0 for Eu citric, 4.5~9.0 for Eu oxine and Eu HIBA, and 6.5~9.0 for Eu 3+ . Eu EDTA can not be adsorbed in the pH range studied. There is large difference in the adsorption behavior on nanometer TiO 2 between rare earth element and its complexes. The possibility of application of nanometer TiO 2 on the speciation of rare earth element was explored.展开更多
Thermodynamic parameters of complexation of naphto- 15-crown-5 with four alkaline earth ions in aqueous media was determined using titration microcalorimetry at 298.15 K. The stability of the complexes, thermal effect...Thermodynamic parameters of complexation of naphto- 15-crown-5 with four alkaline earth ions in aqueous media was determined using titration microcalorimetry at 298.15 K. The stability of the complexes, thermal effect and entropy effect of the complexation is discussed on the basis of the guest ions structure and the solvent effect. The stability constants tendency to vary with ion radius was interpreted. Complex of naphtha-15-crown-5 with calcium ion is very stable due to the synergism of static electric interaction and size selectivity between the host and the guest.展开更多
Some functional lanthanide metal complexes, such as acetylacetonato complexes, ethylenediaminetetraacetato complexes, were successfully applied for diagnostic technique. The authors are interested in investigating the...Some functional lanthanide metal complexes, such as acetylacetonato complexes, ethylenediaminetetraacetato complexes, were successfully applied for diagnostic technique. The authors are interested in investigating the structure and bonding in lanthanide and actinide metal complexes using 166Er, t55Gd, and 237Np Mtissbauer spectroscopies in connection with single-crystal and/or powder X-ray diffraction, making clear the differences on their structures as well as the differences in the participation of 4f and 5f orbitals in the chemical bonds. In this article, the crystal structures of two novel Gd(Ⅲ) acetylacetonato complexes, Gd(pta)3 · 2H2O (pta = 1,1,1 -trifluoro-5,5-dimethy 1-2,4-hexanedione) and Gd(bfa)3 · 2H2O (bfa = 1, 1, 1 -trifluoro-4-phenyl-2-4-butanedione) were reported. Though both of them were dihydrate and had distorted square antiprismatical structure, Gd(pta)3 · 2H2O crystallizes in the P 2 1/n (#14) monoclinic space group and its lattice parameters are a = 1.4141(6) nm, b = 1.0708(3) nm, c =2.2344(4) nm, β =952.4(2)°, and Gd(bfa)3· 2H2O crystallizes in P 212121 orthorhombic space group and its lattice parameters were a = 1.322 (1) nm, b = 2.295 (1) nm, c = 1. 0786(8) nm. In the meantime, the authors had finished a systematic investigation on the ^155Gd Mossbauer isomer shift (δ) of various Gd(Ⅲ) metal complexes having a different coordination number (C.N.) and different ratios coordinating oxygen to nitrogen. A tendency for the 6 value to decrease with an increase in the C.N, and the number of the nitrogen atom coordinating to Gd was confirmed. This indicated that the Gd-O and/or Gd-N bond in the investigated Gd(Ⅲ) metal complexes had a small covalent contribution, which was possible to be deduced from the O and/or N atoms of the lisands donating electrons to 6s, 5d, and 4f orbitals of Gd.展开更多
Comprehensive Summary Four heterometallic rare earth(Ⅲ)-cobalt(Ⅱ)complexes(rare earth=Y(1),Sm(2),Nd(3),La(4))stabilized by an o-phenylenediamine-bridged tris(phenolato)ligand(L)have been synthesized and characterize...Comprehensive Summary Four heterometallic rare earth(Ⅲ)-cobalt(Ⅱ)complexes(rare earth=Y(1),Sm(2),Nd(3),La(4))stabilized by an o-phenylenediamine-bridged tris(phenolato)ligand(L)have been synthesized and characterized.In these tetranuclear complexes,one polydentate L coordinates to one rare earth(Ⅲ)ion,and one cobalt(Ⅱ)ion,respectively,while two rare earth ions are bridged by four acetate groups.These complexes were applied in the copolymerization of cyclohexene oxide and CO_(2),which showed good activity(TON up to 440)and high poly(cyclohexene carbonate)selectivity(>99%).Kinetic studies determined the equation as rate=k[CHO]1[CO_(2)]0[initiator]1,which proves a first-order dependence on initiator concentrations and implies a synergistic mechanism with rare earth and cobalt ions cooperating in epoxide ring-opening and chain propagation.展开更多
Two new alkaline earth metal coordination polymers constructed from the deriva-tive of 1,2,4-triazole are presented herein,namely,{[Sr(AmTAZAc)2(H2O)]}(1) and {[Ba(AmTAZAc)2(H2O)]}(2)(AmTAZAc = 3-amino-1H...Two new alkaline earth metal coordination polymers constructed from the deriva-tive of 1,2,4-triazole are presented herein,namely,{[Sr(AmTAZAc)2(H2O)]}(1) and {[Ba(AmTAZAc)2(H2O)]}(2)(AmTAZAc = 3-amino-1H-1,2,4-triazole-5-carboxylate),which have been synthesized by using the layering method and structurally characterized by elemental analysis,IR,and single-crystal X-ray diffraction.Complexes 1 and 2 are isostructural,and both crystallize in the orthorhombic system,space group Fdd2.X-ray structural analysis shows that 1 or 2 has an intriguing 3-D infinite network of(318.438.510) topology based on a 2-D sheet structure of(4,4) net.The result shows that noncovalent interactions play an important role in strengthening the whole structures of the compounds.展开更多
The strong interatomic interaction effects on photoabsorption cross sections of a private atom have been interpreted by the contribution of both the real and imaginary parts of atomic polarizability in the present wor...The strong interatomic interaction effects on photoabsorption cross sections of a private atom have been interpreted by the contribution of both the real and imaginary parts of atomic polarizability in the present work. Some unresolved differences between the photoabsorption cross sections of isolated atoms and those of condensed atoms, especially near thresholds and resonances, probably could be interpreted by the competition between the imaginary and real parts of atomic frequency-dependent polarizabilities.展开更多
Solvothermal reactions of Ca(NO), Sr(NO)with thiophene-2,5-dicarboxylic in DMF afforded two new inorganic-organic hybrid frameworks, [M(TDC)(DMF)]n(M = Ca(1), Sr(2), TDC = thiophene-2,5-dicarboxylic, DMF = N,N?-dimeth...Solvothermal reactions of Ca(NO), Sr(NO)with thiophene-2,5-dicarboxylic in DMF afforded two new inorganic-organic hybrid frameworks, [M(TDC)(DMF)]n(M = Ca(1), Sr(2), TDC = thiophene-2,5-dicarboxylic, DMF = N,N?-dimethylformamide), which have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis and IR spectra. Both compounds feature three-dimensional(3D) frameworks based on the versatile coordinated modes(μ-η~2:η~2, μ-η~2:η~1, μ-η~2:η~1) of carboxylic groups in tdc ligands. C–H···S hydrogen bonds and C–H···π interactions contribute to the stabilization of the structures. They exhibit weaker packing force compared with their literature isomers. Consequently, blue and blue/green luminescence of two compounds has been observed. Their luminescence mechanism can be ascribed to ligand-to-metal charge transfer(LMCT) compared with the ligand-centered luminescence in their isomers. Electronic structural calculations illustrate that under the condition of weaker packing forces, larger gaps can be achieved, which facilitate the LMCT. This work suggests that the introduction of S-heteroatom can result in more electrons rich in the metal centers, thus giving rise to metal-involved luminescence.展开更多
Photochemical reduction of CO2 with H20 into energy-rich chemicals using inexhaustible solar energy is an appealing strategy to simultaneously address the global energy and environmental issues. Earth-abundant metal c...Photochemical reduction of CO2 with H20 into energy-rich chemicals using inexhaustible solar energy is an appealing strategy to simultaneously address the global energy and environmental issues. Earth-abundant metal complexes show promising application in this field due to their easy availability, rich redox valence and tunable property. Great progress has been seen on catalytic reduction of CO2 under visible light illumination employing earth-abundant metal complexes and their hybrids as key contributors, especially for producing CO and HCOOH via the two-electron reduction process. In this minireview, we will summarize and update advances on earth-abundant metal complex-derived photocatalytic system for visible-light driven CO2 photoreduction over the last 5 years. Homogeneous earth-abundant metal complex photocatalysts and earth-abundant metal complex derived hybrid photocatalysts were both presented with focus on efficient improvement strategy.展开更多
The syndiotactic polymerization of styrene(St) and the copolymerization of St with ethylene(E) were carried out by using a series of chiral half-sandwich rare-earth metal dialkyl complexes(Cp^x*) as the catalys...The syndiotactic polymerization of styrene(St) and the copolymerization of St with ethylene(E) were carried out by using a series of chiral half-sandwich rare-earth metal dialkyl complexes(Cp^x*) as the catalysts. The complexes are Ln(CH2SiMe3)2(THF)(1-4: Ln = Sc(1), Ln = Lu(2), Ln = Y(3), Ln = Dy(4)) bearing chiral cyclopentadienyl ligand containing bulky cylcohexane derivatives in the presence of activator and AliBu3. For the St polymerization, a high activity up to 3.1 × 10^6 g of polymer mol Ln^-1·h^-1 and a high syndiotactic selectivity more than 99% were achieved. The resulting syndiotactic polystyrenes(sPSs) have the molecular weights(Mn) ranging from 3700 g·mol^-1 to 6400 g·mol^-1 and the molecular weight distributions(Mw/Mn) from 1.40 to 5.03. As for the copolymerization of St and E, the activity was up to 2.4 × 10^6 g of copolymer mol Sc^-1·h^-1·MPa^-1, giving random St-E copolymers containing syndiotactic polystyrene sequences with different St content in the range of 15 mol%-58 mol%. These results demonstrate that the bulky cyclopentadienyl ligands of the chiral half-sandwich rare-earth metal complexes effectively inhibit the continued insertion of St monomers into the(co)polymer chain to some extent in comparison with the known half-sandwich rare-earth metal complexes.展开更多
Eleven homobinuclear macrocyclic rare earth metal ions complexes are obtained as com-pounds of 2:2 Schiff base formed by condensing 2,6-diformyl-4-tert-Butylphenol and triethy-lenetetramine by a template procedure usi...Eleven homobinuclear macrocyclic rare earth metal ions complexes are obtained as com-pounds of 2:2 Schiff base formed by condensing 2,6-diformyl-4-tert-Butylphenol and triethy-lenetetramine by a template procedure using rare earth metal isothiocyanates. These complexesare characterized by elemental analyses, FABMS, IR, conductivity and magnetic susceptibility.The variable-temperature magnetic susceptibility (4--300K) of complexes of Gd(Ⅲ) and Tb(Ⅲ) has been determined. A satisfactory fit to theoretical curve derived from spin Hamil-tonian operator was obtained by least squares method. The exchange interaction parameters areJ =-0.220 cm^(-1) for Gd, ,ZJ~?=-0.052 cm^(-1) for Tb. The results indicate a very weak anti-ferromagnetic interaction between Gd^(3+)-Gd^(3+), Tb^(3+)-Tb^(3+) ions.展开更多
Ternary inclusion complexes β-cyclodextrin (β-CD), rare earth metal ions (YbC13, YC13), and 1,8-naphthalene- diamine/ 1,5-naphthalenediamine are synthesized in basic aqueous media, which are characterized via IH...Ternary inclusion complexes β-cyclodextrin (β-CD), rare earth metal ions (YbC13, YC13), and 1,8-naphthalene- diamine/ 1,5-naphthalenediamine are synthesized in basic aqueous media, which are characterized via IH NMR and IR spectroscopy. The stoichiometric proportion of β-CD : YbC13 : 1, 5-naphthalenedia- mine is 2:1:2, that of β-CD:YCI3 : 1,8-naphthalenediamine is 2:1:1, and that of β-CD:YbC13 : 1,8-naphthalenediamine is 2 : 1 : 1. The IR spectroscopy of the ternary inclusion complexes in the range of 935-1 000 cm 1 reveals the existence of the coordinate bond M---O or M---N. The possible conformations of the ternary inclusion complexes are depicted.展开更多
Three new metal complexes derived from Er(Ⅲ), Dy(Ⅲ) and Zr(Ⅳ) with 2-aminobenzohydrazide (ABH) were synthesized and characterized by elemental analyses, IR, ^1H-NMR, ES-MS and transmission electron microsco...Three new metal complexes derived from Er(Ⅲ), Dy(Ⅲ) and Zr(Ⅳ) with 2-aminobenzohydrazide (ABH) were synthesized and characterized by elemental analyses, IR, ^1H-NMR, ES-MS and transmission electron microscopy (TEM). The morphology and the particle size were determined by TEM. The results showed that the ligand acted as neutral bi-dentate coordinating to the metal ions through the carbonyl oxygen and amidic amino nitrogen. The aromatic amine group remained inert towards coordination. The optical band gap was measured and found to be 3.3, 3.5 and 4.3 eV for Er(Ⅲ), Dy(Ⅲ) and Zr(Ⅳ), respectively. The optical band gap values indicated a semi-conducting nature of the investigated complexes. The anti-inflammatory and analgesic activities of the tested compounds were determined and compared with standard meloxicam.展开更多
Four solid complexes of alkaline earth picrates with N,N,N′,N′-tetraphenyl-3,6,9-trioxaundecanediamide (TTD), M (Pic)2TTD (1, M = Mg; 2, M = Ca; 3, M = Sr; 4, M = Ba), have been prepared and characterized by element...Four solid complexes of alkaline earth picrates with N,N,N′,N′-tetraphenyl-3,6,9-trioxaundecanediamide (TTD), M (Pic)2TTD (1, M = Mg; 2, M = Ca; 3, M = Sr; 4, M = Ba), have been prepared and characterized by elemental analysis, conductivity measurement, IR spectra, 1H NMR spectra and TG-DTA techniques. Crystal structure of complex 3 shows that the Sr(II) ion is 9-coordinated by five oxygen atoms from TTD and four oxygen atoms from two bidentate picrates, and the coordination polyhedron is distorted tricapped trigonal prism. TTD as a pentadentate ligand forms a right-handed helical coordination structure. The chelating helical chain has a relative fixed radius and then shows a high coordination selectivity to metal ion. The high selectivity of TTD to alkaline earth ions is explained elementarily from the special coordination structures.展开更多
The reactivities of benzoxazine functionalized amine bridged bis(phenol)s LnH_(2)(n=1—3)with rare earth metal complexes were explored,founding that both the aryl substituents of the ligand and the rare earth metals h...The reactivities of benzoxazine functionalized amine bridged bis(phenol)s LnH_(2)(n=1—3)with rare earth metal complexes were explored,founding that both the aryl substituents of the ligand and the rare earth metals have profound influences on reaction outcomes.展开更多
文摘Complexes of La(Ⅲ),Nd(Ⅲ),Sm(Ⅲ),Eu(Ⅲ),Gd(Ⅲ),Dy(Ⅲ), Er(Ⅲ),Yb(Ⅲ)and Y(Ⅲ)with piperonal isonicotinoyl hydrazone(HPIN) have been synthesized in DMF and EtOH.The complexes have been characte- rized by elemental analysis,molar conductance,i.r.,UV and^1H n.m.r. spectra,magnetic measurements,X-ray powder diffraction and DTA.
文摘A new method of using nanometer TiO 2 as solid phase extractant coupled with ICP AES was proposed for speciation of rare earth elements. The adsorption behavior of rare earth complexes on nanometer TiO 2 was investigated. Effect of pH value, contact time, elution solution and interfering ions on the recovery of the rare earth complexes were studied. A quantitative recovery (>90%) was found in the pH range of 4~9.0 for Eu citric, 4.5~9.0 for Eu oxine and Eu HIBA, and 6.5~9.0 for Eu 3+ . Eu EDTA can not be adsorbed in the pH range studied. There is large difference in the adsorption behavior on nanometer TiO 2 between rare earth element and its complexes. The possibility of application of nanometer TiO 2 on the speciation of rare earth element was explored.
文摘Thermodynamic parameters of complexation of naphto- 15-crown-5 with four alkaline earth ions in aqueous media was determined using titration microcalorimetry at 298.15 K. The stability of the complexes, thermal effect and entropy effect of the complexation is discussed on the basis of the guest ions structure and the solvent effect. The stability constants tendency to vary with ion radius was interpreted. Complex of naphtha-15-crown-5 with calcium ion is very stable due to the synergism of static electric interaction and size selectivity between the host and the guest.
基金Project supported by the Grants-in-Aid for Scientific Research from the Ministry of Education, Science and Culture, Japan andin Part by the Inter-University Joint Research Program for the Common Use of JAERI (Japan Atomic Energy Research Institute)Facilities
文摘Some functional lanthanide metal complexes, such as acetylacetonato complexes, ethylenediaminetetraacetato complexes, were successfully applied for diagnostic technique. The authors are interested in investigating the structure and bonding in lanthanide and actinide metal complexes using 166Er, t55Gd, and 237Np Mtissbauer spectroscopies in connection with single-crystal and/or powder X-ray diffraction, making clear the differences on their structures as well as the differences in the participation of 4f and 5f orbitals in the chemical bonds. In this article, the crystal structures of two novel Gd(Ⅲ) acetylacetonato complexes, Gd(pta)3 · 2H2O (pta = 1,1,1 -trifluoro-5,5-dimethy 1-2,4-hexanedione) and Gd(bfa)3 · 2H2O (bfa = 1, 1, 1 -trifluoro-4-phenyl-2-4-butanedione) were reported. Though both of them were dihydrate and had distorted square antiprismatical structure, Gd(pta)3 · 2H2O crystallizes in the P 2 1/n (#14) monoclinic space group and its lattice parameters are a = 1.4141(6) nm, b = 1.0708(3) nm, c =2.2344(4) nm, β =952.4(2)°, and Gd(bfa)3· 2H2O crystallizes in P 212121 orthorhombic space group and its lattice parameters were a = 1.322 (1) nm, b = 2.295 (1) nm, c = 1. 0786(8) nm. In the meantime, the authors had finished a systematic investigation on the ^155Gd Mossbauer isomer shift (δ) of various Gd(Ⅲ) metal complexes having a different coordination number (C.N.) and different ratios coordinating oxygen to nitrogen. A tendency for the 6 value to decrease with an increase in the C.N, and the number of the nitrogen atom coordinating to Gd was confirmed. This indicated that the Gd-O and/or Gd-N bond in the investigated Gd(Ⅲ) metal complexes had a small covalent contribution, which was possible to be deduced from the O and/or N atoms of the lisands donating electrons to 6s, 5d, and 4f orbitals of Gd.
基金financial support from the National Natural Science Foundation of China(21871198)the Major Research Project of the Natural Science of the Jiangsu Higher Education Institutions(19KJA360005 and 19KJA320007),and PAPD.
文摘Comprehensive Summary Four heterometallic rare earth(Ⅲ)-cobalt(Ⅱ)complexes(rare earth=Y(1),Sm(2),Nd(3),La(4))stabilized by an o-phenylenediamine-bridged tris(phenolato)ligand(L)have been synthesized and characterized.In these tetranuclear complexes,one polydentate L coordinates to one rare earth(Ⅲ)ion,and one cobalt(Ⅱ)ion,respectively,while two rare earth ions are bridged by four acetate groups.These complexes were applied in the copolymerization of cyclohexene oxide and CO_(2),which showed good activity(TON up to 440)and high poly(cyclohexene carbonate)selectivity(>99%).Kinetic studies determined the equation as rate=k[CHO]1[CO_(2)]0[initiator]1,which proves a first-order dependence on initiator concentrations and implies a synergistic mechanism with rare earth and cobalt ions cooperating in epoxide ring-opening and chain propagation.
基金Supported by the National Natural Science Foundation of China (Nos. 20771006 and 20901004)
文摘Two new alkaline earth metal coordination polymers constructed from the deriva-tive of 1,2,4-triazole are presented herein,namely,{[Sr(AmTAZAc)2(H2O)]}(1) and {[Ba(AmTAZAc)2(H2O)]}(2)(AmTAZAc = 3-amino-1H-1,2,4-triazole-5-carboxylate),which have been synthesized by using the layering method and structurally characterized by elemental analysis,IR,and single-crystal X-ray diffraction.Complexes 1 and 2 are isostructural,and both crystallize in the orthorhombic system,space group Fdd2.X-ray structural analysis shows that 1 or 2 has an intriguing 3-D infinite network of(318.438.510) topology based on a 2-D sheet structure of(4,4) net.The result shows that noncovalent interactions play an important role in strengthening the whole structures of the compounds.
基金Project partly supported by the University Science & Technology Planning Program of Shandong Province of China (Grant No. J10LB60)Discipline Construction Fund and 2009 Technology Innovation Fund of Ludong University (Grant No. 09L026)
文摘The strong interatomic interaction effects on photoabsorption cross sections of a private atom have been interpreted by the contribution of both the real and imaginary parts of atomic polarizability in the present work. Some unresolved differences between the photoabsorption cross sections of isolated atoms and those of condensed atoms, especially near thresholds and resonances, probably could be interpreted by the competition between the imaginary and real parts of atomic frequency-dependent polarizabilities.
基金supported by the Science and Technology Funding Project of Fujian Provincial Department of Transportation(No.201337)
文摘Solvothermal reactions of Ca(NO), Sr(NO)with thiophene-2,5-dicarboxylic in DMF afforded two new inorganic-organic hybrid frameworks, [M(TDC)(DMF)]n(M = Ca(1), Sr(2), TDC = thiophene-2,5-dicarboxylic, DMF = N,N?-dimethylformamide), which have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis and IR spectra. Both compounds feature three-dimensional(3D) frameworks based on the versatile coordinated modes(μ-η~2:η~2, μ-η~2:η~1, μ-η~2:η~1) of carboxylic groups in tdc ligands. C–H···S hydrogen bonds and C–H···π interactions contribute to the stabilization of the structures. They exhibit weaker packing force compared with their literature isomers. Consequently, blue and blue/green luminescence of two compounds has been observed. Their luminescence mechanism can be ascribed to ligand-to-metal charge transfer(LMCT) compared with the ligand-centered luminescence in their isomers. Electronic structural calculations illustrate that under the condition of weaker packing forces, larger gaps can be achieved, which facilitate the LMCT. This work suggests that the introduction of S-heteroatom can result in more electrons rich in the metal centers, thus giving rise to metal-involved luminescence.
文摘Photochemical reduction of CO2 with H20 into energy-rich chemicals using inexhaustible solar energy is an appealing strategy to simultaneously address the global energy and environmental issues. Earth-abundant metal complexes show promising application in this field due to their easy availability, rich redox valence and tunable property. Great progress has been seen on catalytic reduction of CO2 under visible light illumination employing earth-abundant metal complexes and their hybrids as key contributors, especially for producing CO and HCOOH via the two-electron reduction process. In this minireview, we will summarize and update advances on earth-abundant metal complex-derived photocatalytic system for visible-light driven CO2 photoreduction over the last 5 years. Homogeneous earth-abundant metal complex photocatalysts and earth-abundant metal complex derived hybrid photocatalysts were both presented with focus on efficient improvement strategy.
基金financially supported by the National Natural Science Foundation of China (Nos. 20974014, 21274012, 21322401 and 21774014)the 111 project (No. B07012)
文摘The syndiotactic polymerization of styrene(St) and the copolymerization of St with ethylene(E) were carried out by using a series of chiral half-sandwich rare-earth metal dialkyl complexes(Cp^x*) as the catalysts. The complexes are Ln(CH2SiMe3)2(THF)(1-4: Ln = Sc(1), Ln = Lu(2), Ln = Y(3), Ln = Dy(4)) bearing chiral cyclopentadienyl ligand containing bulky cylcohexane derivatives in the presence of activator and AliBu3. For the St polymerization, a high activity up to 3.1 × 10^6 g of polymer mol Ln^-1·h^-1 and a high syndiotactic selectivity more than 99% were achieved. The resulting syndiotactic polystyrenes(sPSs) have the molecular weights(Mn) ranging from 3700 g·mol^-1 to 6400 g·mol^-1 and the molecular weight distributions(Mw/Mn) from 1.40 to 5.03. As for the copolymerization of St and E, the activity was up to 2.4 × 10^6 g of copolymer mol Sc^-1·h^-1·MPa^-1, giving random St-E copolymers containing syndiotactic polystyrene sequences with different St content in the range of 15 mol%-58 mol%. These results demonstrate that the bulky cyclopentadienyl ligands of the chiral half-sandwich rare-earth metal complexes effectively inhibit the continued insertion of St monomers into the(co)polymer chain to some extent in comparison with the known half-sandwich rare-earth metal complexes.
基金Project supported by the National Natural Science Foundation of China.
文摘Eleven homobinuclear macrocyclic rare earth metal ions complexes are obtained as com-pounds of 2:2 Schiff base formed by condensing 2,6-diformyl-4-tert-Butylphenol and triethy-lenetetramine by a template procedure using rare earth metal isothiocyanates. These complexesare characterized by elemental analyses, FABMS, IR, conductivity and magnetic susceptibility.The variable-temperature magnetic susceptibility (4--300K) of complexes of Gd(Ⅲ) and Tb(Ⅲ) has been determined. A satisfactory fit to theoretical curve derived from spin Hamil-tonian operator was obtained by least squares method. The exchange interaction parameters areJ =-0.220 cm^(-1) for Gd, ,ZJ~?=-0.052 cm^(-1) for Tb. The results indicate a very weak anti-ferromagnetic interaction between Gd^(3+)-Gd^(3+), Tb^(3+)-Tb^(3+) ions.
基金Supported by the Project of Education Department of Liaoning Province (20040084)
文摘Ternary inclusion complexes β-cyclodextrin (β-CD), rare earth metal ions (YbC13, YC13), and 1,8-naphthalene- diamine/ 1,5-naphthalenediamine are synthesized in basic aqueous media, which are characterized via IH NMR and IR spectroscopy. The stoichiometric proportion of β-CD : YbC13 : 1, 5-naphthalenedia- mine is 2:1:2, that of β-CD:YCI3 : 1,8-naphthalenediamine is 2:1:1, and that of β-CD:YbC13 : 1,8-naphthalenediamine is 2 : 1 : 1. The IR spectroscopy of the ternary inclusion complexes in the range of 935-1 000 cm 1 reveals the existence of the coordinate bond M---O or M---N. The possible conformations of the ternary inclusion complexes are depicted.
文摘Three new metal complexes derived from Er(Ⅲ), Dy(Ⅲ) and Zr(Ⅳ) with 2-aminobenzohydrazide (ABH) were synthesized and characterized by elemental analyses, IR, ^1H-NMR, ES-MS and transmission electron microscopy (TEM). The morphology and the particle size were determined by TEM. The results showed that the ligand acted as neutral bi-dentate coordinating to the metal ions through the carbonyl oxygen and amidic amino nitrogen. The aromatic amine group remained inert towards coordination. The optical band gap was measured and found to be 3.3, 3.5 and 4.3 eV for Er(Ⅲ), Dy(Ⅲ) and Zr(Ⅳ), respectively. The optical band gap values indicated a semi-conducting nature of the investigated complexes. The anti-inflammatory and analgesic activities of the tested compounds were determined and compared with standard meloxicam.
基金This work was supported by the National Natural Science Foundation of China(Grant No.20071015)Key Project of Science and Technology of the Ministry of Education of China(Grant No.01170)Foundation for University Key Teacher by the Ministry of Education of China.
文摘Four solid complexes of alkaline earth picrates with N,N,N′,N′-tetraphenyl-3,6,9-trioxaundecanediamide (TTD), M (Pic)2TTD (1, M = Mg; 2, M = Ca; 3, M = Sr; 4, M = Ba), have been prepared and characterized by elemental analysis, conductivity measurement, IR spectra, 1H NMR spectra and TG-DTA techniques. Crystal structure of complex 3 shows that the Sr(II) ion is 9-coordinated by five oxygen atoms from TTD and four oxygen atoms from two bidentate picrates, and the coordination polyhedron is distorted tricapped trigonal prism. TTD as a pentadentate ligand forms a right-handed helical coordination structure. The chelating helical chain has a relative fixed radius and then shows a high coordination selectivity to metal ion. The high selectivity of TTD to alkaline earth ions is explained elementarily from the special coordination structures.
基金support fromtheNational Natural Science Foundation of China(21871198)the Major Research Project of the Natural Science of the Jiangsu Higher Education Institutions(19KJA360005),and PAPD.
文摘The reactivities of benzoxazine functionalized amine bridged bis(phenol)s LnH_(2)(n=1—3)with rare earth metal complexes were explored,founding that both the aryl substituents of the ligand and the rare earth metals have profound influences on reaction outcomes.