Studies on the electronic structure,molecular design,syntheses of some novel series of tetranuclear rare earth complexes in our laboratory have been reviewed.Spin-unrestricted localized INDO method was used to calcula...Studies on the electronic structure,molecular design,syntheses of some novel series of tetranuclear rare earth complexes in our laboratory have been reviewed.Spin-unrestricted localized INDO method was used to calculate the electronic structure and the chemical bonding in the typical rare earth cluster Sc[Sc_6Cl_(12)Co]was discussed.展开更多
[HoAl(CF_3COO)_2(CF_3CHOO)(C_2H_5)_2(C_4H_8O)_2]_2,Mr=1468.7,monoclinic,P 2_1/n,a=1.0084(4), b=1.8453(6),c=1.4501(6)nm,β=102.40(3)°,V=2.6355(1)nm^3,Z=2,D_c=1.81gcm^(-3),F(000)=1511, T=233K,Mo Kα radiation(λ=0....[HoAl(CF_3COO)_2(CF_3CHOO)(C_2H_5)_2(C_4H_8O)_2]_2,Mr=1468.7,monoclinic,P 2_1/n,a=1.0084(4), b=1.8453(6),c=1.4501(6)nm,β=102.40(3)°,V=2.6355(1)nm^3,Z=2,D_c=1.81gcm^(-3),F(000)=1511, T=233K,Mo Kα radiation(λ=0.071069nm).R=0.052 for 6176 unique reflections[Ⅰ≥36(Ⅰ)].The structural units consist of dimeric molecules with the mixed ligand and central bimetallic atoms,which are polynuclear lanthanoid complexes containing aluminium.Ho-Ho'distance is 0.3619(1)nm.The coordination polyhedron of Ho can be described in terms of a distored bicap-prism.展开更多
Five complexes of copper and lanthanide series containing iminodiacetic group Hgands have been synthesized and investigated. The structures of three compounds have been determined by X-ray single crystal diffraction. ...Five complexes of copper and lanthanide series containing iminodiacetic group Hgands have been synthesized and investigated. The structures of three compounds have been determined by X-ray single crystal diffraction. Their vibrational spectra have been measured and assigned rationally.展开更多
In an acidic solution the mixed polynuclear complexes could be formed by association of rareearth-arsenazo Ⅲ complexing anions with copper o-phenanthrolinate cations.In this paper the formationconditions of lanthanum...In an acidic solution the mixed polynuclear complexes could be formed by association of rareearth-arsenazo Ⅲ complexing anions with copper o-phenanthrolinate cations.In this paper the formationconditions of lanthanum-arsenazo Ⅲ-copper-o-phenanthroline complex and its related reaction mechanismhave been studied in detail.The complex exhibits an absorption maximum at 663 nm and its apparent molarabsorptivity is found to be 1.22×105L·mol-1·cm-1.The molar ratio of the components in the complex isestimated to be La:arsenazo Ⅲ:Cu:Phen=1:1:1:3.Its possible molecular formula can expressed as[Cu（Phen）3]（La-arsenazo Ⅲ）.The reaction is used to determine micro amounts of lanthanum（or rareearths）in copper containning synthetic samples and satisfactory results are obtained.展开更多
A novel method was described for the determination of ultra trace amount of scandium based on the cathodic adsorptive voltammetry of the mix-polynuclear complex of scandium-calcium-alizarin red S at a carbon paste ele...A novel method was described for the determination of ultra trace amount of scandium based on the cathodic adsorptive voltammetry of the mix-polynuclear complex of scandium-calcium-alizarin red S at a carbon paste electrode (CPE). The 2nd-order derivative linear scan voltammograms of the adsorbed complex were recorded by model JP-303 polarographic analyzer from 0.0 to -1.0 V (vs. SCE). The experimental conditions of the working procedure were optimized. The results show that the complex can be adsorbed on the surface of the CPE, yielding one peak at -0.61 V, corresponding to the reduction of the alizarin red S in the mix-polynuclear complex at the electrode. The detection limit of Sc^(3+) is 1.0×10^(-10) mol·L^(-1) for 3 min of accumulation time. The procedure was successfully applied to the determination of trace amount of scandium in the sample ores.展开更多
Five polynuclear monovalent and mixed-valence complexes of copper with 2-thiouracil were synthesized. They were characterized by the molar conductivity, electromc spectra, infrared spectroscopy, thermogravimetric and ...Five polynuclear monovalent and mixed-valence complexes of copper with 2-thiouracil were synthesized. They were characterized by the molar conductivity, electromc spectra, infrared spectroscopy, thermogravimetric and magnetic susceptibility measurements. Their coordination properties and tentative structures were discussed.展开更多
The polynuclear complex, [La(bphsb) 2(NO 3) 3] n (bphsb=1,4 bis(phenylsulfinyl)butane) were obtained. The structure of the complex consists of ten coordinated metal ions linked up with six O atoms of the thre...The polynuclear complex, [La(bphsb) 2(NO 3) 3] n (bphsb=1,4 bis(phenylsulfinyl)butane) were obtained. The structure of the complex consists of ten coordinated metal ions linked up with six O atoms of the three bidentate nitrates and with four O atoms of the four bphsb ligands. The coordination polyhedron of the La 3+ may best be described as distorted bicapped square antiprism. The bphsb ligands act as bridges that join two neighbouring lanthanum ions to give polymeric chains. Each chain contains 18 membered macrocyclic rings with two La atoms. In the complex, the bphsb ligands adopt meso stereoisomer in which sulfur atoms are chiral, and the absolute configurations of the atoms are RS.展开更多
A novel polymeric complex [La(bipyN2O2)(TFA)3]n(TFA= trifluoroacetylacetone) was prepared. The X-ray structure analysis revealed that the complex has an infinite one-dimensional supramolecule structure with the 4,4...A novel polymeric complex [La(bipyN2O2)(TFA)3]n(TFA= trifluoroacetylacetone) was prepared. The X-ray structure analysis revealed that the complex has an infinite one-dimensional supramolecule structure with the 4,4'-bipyridyl-N,N'-dioxide as a bridge. La(III) is coordinated to eight oxygen atoms, six from three trifluoroacetylacetonate anions, two from two 4,4'-bipyridyl-N,N'-dioxide molecules.展开更多
The synthesis, characterization of five ditopic or tritopic crown compounds were reported in this paper together with the preparation of the corresponding hetero-dinuclear and hetero-trinuclear complexes with differen...The synthesis, characterization of five ditopic or tritopic crown compounds were reported in this paper together with the preparation of the corresponding hetero-dinuclear and hetero-trinuclear complexes with different metal cations.展开更多
The organic-inorganic hybrid complex with formula [（CuL）2Cu3（μ-1,1-N3）4（ClO4）2], complex 1, {CuL, [5,6：14,l5-dibenzo-1,4,8,12-tetraazacyclopentadeca-7,3-diene-2,3-dione（2-）]copper（Ⅱ）}, has been synthesize...The organic-inorganic hybrid complex with formula [（CuL）2Cu3（μ-1,1-N3）4（ClO4）2], complex 1, {CuL, [5,6：14,l5-dibenzo-1,4,8,12-tetraazacyclopentadeca-7,3-diene-2,3-dione（2-）]copper（Ⅱ）}, has been synthesized and structurally determined. The crystals of complex 1 crystallize in the triclinic system with space group P1, a=0.92983（12） nm, b=1.09644（14） nm, c=1.27396（16） nm, α=70.782（2）°β=86.266（2）°,γ=78.284（2）°. In this complex, the five copper ions are bridged by macrocyclic oxamide groups and azido. Furthermore, C-H…O hydrogen bond interactions link the pentanuclear fragments to form a 2D supramolecular architecture.展开更多
The synthesis, structure and characterization of a new one-dimensional cyanide-bridgedcomplex [Ni(pn)_2Ni(CN)4]n'nH2O (where pn = 1,2-diaminopropane) are described. The structure ofthis complex consists of a one-d...The synthesis, structure and characterization of a new one-dimensional cyanide-bridgedcomplex [Ni(pn)_2Ni(CN)4]n'nH2O (where pn = 1,2-diaminopropane) are described. The structure ofthis complex consists of a one-dimensional polymeric chain-Ni(pn)2-NC-Ni(CN)2-CN-Ni(pn)2- inwhich the Ni(II) centers are linked by two CN groups.展开更多
The complexes [Pt2L2（μ-dppm）]（ClO4）2 （1） and {[Pt2L2（μ-dppm）Li（CH3CN）2]（ClO4）3}n （2）, where HL is 6-[4-（diethoxyphosphorylmethyl）phenyl]-2,2′-bipyridinyl and dppm is bis（diphenylphosphino）methane,...The complexes [Pt2L2（μ-dppm）]（ClO4）2 （1） and {[Pt2L2（μ-dppm）Li（CH3CN）2]（ClO4）3}n （2）, where HL is 6-[4-（diethoxyphosphorylmethyl）phenyl]-2,2′-bipyridinyl and dppm is bis（diphenylphosphino）methane, have been synthesized and characterized. In complex 1 the platinum（Ⅱ） center adopts a distorted square planar coordination geometry. The polymer 2 exhibits a ＂stairstep＂ configuration with one-dimensional Pt（Ⅱ）N^N^CPO- Li（Ⅰ）-OPC^N^ NPt（Ⅱ） mixed-metal units which are linked through dppm. Both complexes have metal-metal interaction with Pt- Pt distances of 3.325（2） and 3.1432（9） A, respectively, and display strong metal-metal-to-ligand charge-transfer （MMLCT） triplet state emission. The density-functional-theory calculation was used to interpret the absorption spectra of the complexes.展开更多
In the preceding work we discussed the formation of mixed polynuclear complexes (MPC) of rare earth-arsenazo Ⅲ-copper-o-phenanthroline. This note reports the action rule of various 2, 7-bisazochromotropic acid dyes w...In the preceding work we discussed the formation of mixed polynuclear complexes (MPC) of rare earth-arsenazo Ⅲ-copper-o-phenanthroline. This note reports the action rule of various 2, 7-bisazochromotropic acid dyes with different structures in this kind of colour reactions. The experiments showed that only those symmetric 2, 7-bisazochromotropic展开更多
Three metal ion bridged self-assembled （SA） films of cis-di（thiocyanato）-bis（2,2＇-bipyridyl-4,4＇-dicarboxylate） ruthenium were fabricated and characterized by contact angle, UV spectra, cyclic voltammetry and ...Three metal ion bridged self-assembled （SA） films of cis-di（thiocyanato）-bis（2,2＇-bipyridyl-4,4＇-dicarboxylate） ruthenium were fabricated and characterized by contact angle, UV spectra, cyclic voltammetry and XPS. Their photoinduced electron transfer properties （PETP） were examined. Among the titled systems, the highest steady anodic photocurrent of 1773-1843 nA/cm^2 and the highest quantum yield of 3.2% were achieved. The effects of incident light intensity, bias voltage, and electron donor were also studied. The possible mechanism of electron transfer was proposed. The results reveal that different metal ion in SA films could affect significantly the photoinduced electron transfer property. Our experimental results clearly show that bridging metal ions can play both functional and structural roles in these self-assembled systems. This method of forming functional films can provide a new approach to regulate the property of similar systems.展开更多
Polynuclear gold complexes show diverse structures and bonding.An exploration into their transformation represents a challenging area of research.Herein,an unprecedented substituent-mediated transformation from pentag...Polynuclear gold complexes show diverse structures and bonding.An exploration into their transformation represents a challenging area of research.Herein,an unprecedented substituent-mediated transformation from pentagold(I)to octadecagold(I)complexes has been observed.These gold(I)-sulfido complexes with distinct structures have been fully characterized,and the transformation process has been monitored by NMR spectroscopy in solution state.展开更多
基金Project supported by The National Natural Science Foundation of China and Science and Technology Foundation of State Education Commision of China
文摘Studies on the electronic structure,molecular design,syntheses of some novel series of tetranuclear rare earth complexes in our laboratory have been reviewed.Spin-unrestricted localized INDO method was used to calculate the electronic structure and the chemical bonding in the typical rare earth cluster Sc[Sc_6Cl_(12)Co]was discussed.
文摘[HoAl(CF_3COO)_2(CF_3CHOO)(C_2H_5)_2(C_4H_8O)_2]_2,Mr=1468.7,monoclinic,P 2_1/n,a=1.0084(4), b=1.8453(6),c=1.4501(6)nm,β=102.40(3)°,V=2.6355(1)nm^3,Z=2,D_c=1.81gcm^(-3),F(000)=1511, T=233K,Mo Kα radiation(λ=0.071069nm).R=0.052 for 6176 unique reflections[Ⅰ≥36(Ⅰ)].The structural units consist of dimeric molecules with the mixed ligand and central bimetallic atoms,which are polynuclear lanthanoid complexes containing aluminium.Ho-Ho'distance is 0.3619(1)nm.The coordination polyhedron of Ho can be described in terms of a distored bicap-prism.
文摘Five complexes of copper and lanthanide series containing iminodiacetic group Hgands have been synthesized and investigated. The structures of three compounds have been determined by X-ray single crystal diffraction. Their vibrational spectra have been measured and assigned rationally.
文摘In an acidic solution the mixed polynuclear complexes could be formed by association of rareearth-arsenazo Ⅲ complexing anions with copper o-phenanthrolinate cations.In this paper the formationconditions of lanthanum-arsenazo Ⅲ-copper-o-phenanthroline complex and its related reaction mechanismhave been studied in detail.The complex exhibits an absorption maximum at 663 nm and its apparent molarabsorptivity is found to be 1.22×105L·mol-1·cm-1.The molar ratio of the components in the complex isestimated to be La:arsenazo Ⅲ:Cu:Phen=1:1:1:3.Its possible molecular formula can expressed as[Cu（Phen）3]（La-arsenazo Ⅲ）.The reaction is used to determine micro amounts of lanthanum（or rareearths）in copper containning synthetic samples and satisfactory results are obtained.
文摘A novel method was described for the determination of ultra trace amount of scandium based on the cathodic adsorptive voltammetry of the mix-polynuclear complex of scandium-calcium-alizarin red S at a carbon paste electrode (CPE). The 2nd-order derivative linear scan voltammograms of the adsorbed complex were recorded by model JP-303 polarographic analyzer from 0.0 to -1.0 V (vs. SCE). The experimental conditions of the working procedure were optimized. The results show that the complex can be adsorbed on the surface of the CPE, yielding one peak at -0.61 V, corresponding to the reduction of the alizarin red S in the mix-polynuclear complex at the electrode. The detection limit of Sc^(3+) is 1.0×10^(-10) mol·L^(-1) for 3 min of accumulation time. The procedure was successfully applied to the determination of trace amount of scandium in the sample ores.
文摘Five polynuclear monovalent and mixed-valence complexes of copper with 2-thiouracil were synthesized. They were characterized by the molar conductivity, electromc spectra, infrared spectroscopy, thermogravimetric and magnetic susceptibility measurements. Their coordination properties and tentative structures were discussed.
文摘The polynuclear complex, [La(bphsb) 2(NO 3) 3] n (bphsb=1,4 bis(phenylsulfinyl)butane) were obtained. The structure of the complex consists of ten coordinated metal ions linked up with six O atoms of the three bidentate nitrates and with four O atoms of the four bphsb ligands. The coordination polyhedron of the La 3+ may best be described as distorted bicapped square antiprism. The bphsb ligands act as bridges that join two neighbouring lanthanum ions to give polymeric chains. Each chain contains 18 membered macrocyclic rings with two La atoms. In the complex, the bphsb ligands adopt meso stereoisomer in which sulfur atoms are chiral, and the absolute configurations of the atoms are RS.
基金The National Natural Science Foundation of China.
文摘A novel polymeric complex [La(bipyN2O2)(TFA)3]n(TFA= trifluoroacetylacetone) was prepared. The X-ray structure analysis revealed that the complex has an infinite one-dimensional supramolecule structure with the 4,4'-bipyridyl-N,N'-dioxide as a bridge. La(III) is coordinated to eight oxygen atoms, six from three trifluoroacetylacetonate anions, two from two 4,4'-bipyridyl-N,N'-dioxide molecules.
基金the National Natural Science Foundation of China (29872034) and the Natural Science Foundation of Henan Province for the financi
文摘The synthesis, characterization of five ditopic or tritopic crown compounds were reported in this paper together with the preparation of the corresponding hetero-dinuclear and hetero-trinuclear complexes with different metal cations.
基金Supported by the National Natural Science Foundation of China(No.20771083)
文摘The organic-inorganic hybrid complex with formula [（CuL）2Cu3（μ-1,1-N3）4（ClO4）2], complex 1, {CuL, [5,6：14,l5-dibenzo-1,4,8,12-tetraazacyclopentadeca-7,3-diene-2,3-dione（2-）]copper（Ⅱ）}, has been synthesized and structurally determined. The crystals of complex 1 crystallize in the triclinic system with space group P1, a=0.92983（12） nm, b=1.09644（14） nm, c=1.27396（16） nm, α=70.782（2）°β=86.266（2）°,γ=78.284（2）°. In this complex, the five copper ions are bridged by macrocyclic oxamide groups and azido. Furthermore, C-H…O hydrogen bond interactions link the pentanuclear fragments to form a 2D supramolecular architecture.
文摘The synthesis, structure and characterization of a new one-dimensional cyanide-bridgedcomplex [Ni(pn)_2Ni(CN)4]n'nH2O (where pn = 1,2-diaminopropane) are described. The structure ofthis complex consists of a one-dimensional polymeric chain-Ni(pn)2-NC-Ni(CN)2-CN-Ni(pn)2- inwhich the Ni(II) centers are linked by two CN groups.
文摘The complexes [Pt2L2（μ-dppm）]（ClO4）2 （1） and {[Pt2L2（μ-dppm）Li（CH3CN）2]（ClO4）3}n （2）, where HL is 6-[4-（diethoxyphosphorylmethyl）phenyl]-2,2′-bipyridinyl and dppm is bis（diphenylphosphino）methane, have been synthesized and characterized. In complex 1 the platinum（Ⅱ） center adopts a distorted square planar coordination geometry. The polymer 2 exhibits a ＂stairstep＂ configuration with one-dimensional Pt（Ⅱ）N^N^CPO- Li（Ⅰ）-OPC^N^ NPt（Ⅱ） mixed-metal units which are linked through dppm. Both complexes have metal-metal interaction with Pt- Pt distances of 3.325（2） and 3.1432（9） A, respectively, and display strong metal-metal-to-ligand charge-transfer （MMLCT） triplet state emission. The density-functional-theory calculation was used to interpret the absorption spectra of the complexes.
基金Project supported by the National Natural Science Foundation of China (1988-1990).
文摘In the preceding work we discussed the formation of mixed polynuclear complexes (MPC) of rare earth-arsenazo Ⅲ-copper-o-phenanthroline. This note reports the action rule of various 2, 7-bisazochromotropic acid dyes with different structures in this kind of colour reactions. The experiments showed that only those symmetric 2, 7-bisazochromotropic
基金Project supported by the National NaturaJ Science Foundation of China （Nos. 20471009, 20573010）, the Scientific Research Foundation for the Returned 0verseas Chinese Scholars, State Education Ministry, Excellent Young Scholars Research Fund of Beijing Institute of Technology （No. 000Y07-30）.
文摘Three metal ion bridged self-assembled （SA） films of cis-di（thiocyanato）-bis（2,2＇-bipyridyl-4,4＇-dicarboxylate） ruthenium were fabricated and characterized by contact angle, UV spectra, cyclic voltammetry and XPS. Their photoinduced electron transfer properties （PETP） were examined. Among the titled systems, the highest steady anodic photocurrent of 1773-1843 nA/cm^2 and the highest quantum yield of 3.2% were achieved. The effects of incident light intensity, bias voltage, and electron donor were also studied. The possible mechanism of electron transfer was proposed. The results reveal that different metal ion in SA films could affect significantly the photoinduced electron transfer property. Our experimental results clearly show that bridging metal ions can play both functional and structural roles in these self-assembled systems. This method of forming functional films can provide a new approach to regulate the property of similar systems.
基金The University of Hong Kong for supporting the Electrospray Ionization Quadrupole Time-of-Flight Mass Spectrometry Facilities under the Support for Interdisciplinary Research in Chemical Science and the support from The University of Hong Kong under the University Research Committee(URC)Strategically Oriented Research Theme on Functional Materials for Molecular Electronicsthe Key Program of the Major Research Plan on“Architectures,Functionalities and Evolution of Hierarchical Clusters”of the National Natural Science Foundation of China(grant no.91961202)and a General Research Fund(GRF)from the Research Grants Council of Hong Kong Special Administrative Region,China(HKU17301517).L.-L.Y.acknowledges the receipt of a postgraduate studentship from The University of Hong Kong.The Beijing Synchrotron Research Facility(BSRF)is also acknowledged for providing beamline time of the synchrotron radiation X-ray diffraction facilities.
文摘Polynuclear gold complexes show diverse structures and bonding.An exploration into their transformation represents a challenging area of research.Herein,an unprecedented substituent-mediated transformation from pentagold(I)to octadecagold(I)complexes has been observed.These gold(I)-sulfido complexes with distinct structures have been fully characterized,and the transformation process has been monitored by NMR spectroscopy in solution state.
