The single crystal of the complex [Sc(NO_3)_3(H_2O)_2]·(15C5) has been prepared in acetonitrile.The new complex has been characterized by elemental analysis,IR spectra,solubility and molar conductance measurement...The single crystal of the complex [Sc(NO_3)_3(H_2O)_2]·(15C5) has been prepared in acetonitrile.The new complex has been characterized by elemental analysis,IR spectra,solubility and molar conductance measurements.The structure of the complex is determined by single crystal X-ray diffraction analysis.展开更多
A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemic...A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemical calculation.The calculated results are in good agreement with that obtained in the experiments.Three Cl atoms are on the same side of Ln in LnCl_3·15-C-5 and the crown ring on the other side.forming a complex molecule with coordination number 8.LnCl_3·15-C-5 is easily hygroscopic in air because of its unsaturated coordination,which differs sharply from the stable Ln(NO_3)_3·15-C-5 com- plex of coordination number 11.The HOMO and neighboring occupied MOs are composed of Cl 3p and O2p, and the LUMO and neighboring unoccupied MOs are composed of Ln orbitals.The level structure easily pro- duces Ln3d satellite in XPS caused by L→Ln charge transfer transition.Due to the coordination,the absolute values of the charge are decreased at Ln and O atoms,but increased at Cl atoms,which is in agreement with XPS results.展开更多
Three new solid complexes of macrocyclic polyether ligand 2, 2'-dinitro-4, 5, 4', 5'bis-(15- crown-5)-dihenzo disulfide(L) with trivalent rare earth nitrates having composition of RE(NO_3)_3·L ·6...Three new solid complexes of macrocyclic polyether ligand 2, 2'-dinitro-4, 5, 4', 5'bis-(15- crown-5)-dihenzo disulfide(L) with trivalent rare earth nitrates having composition of RE(NO_3)_3·L ·6H_2O(RE=Ce, Pr, Nd) have been synthesized in acetonitrile. All the isolated complexes have been characterized by elementary analysis, IR and UV spectra, differential thermal and thermogravimetric analysis, X-ray powder diffraction analysis, molar conductance and measurements of solubility in some general solvents.展开更多
Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,B...Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,Bu,m=0.1,n=1,4)have been synthesized in acetonitrile or acetone.All the isolated complexes have been char- acterized by elementary analysis,IR and UV spectra,differential thermal and thermogravimetric analysis,X-ray powder diffraction analysis,molar conductance and measurementa of solubility in some general solventa.It shows that coordination number of the rare earth cation in the complexes of La,Ce,Pr and Nd nitrate is eleven.展开更多
The interaction of lanthanum(Ⅲ) chloride with 12-crown-4 in MeCN/MeOH mixed solvent produces an anhydrous complex,LaCl3(12-crown-4)(MeOH)(complex Ⅰ),C9H20O5LaCl3(Mr= 453.6),in which the La(Ⅲ) ion is 8-coordinated b...The interaction of lanthanum(Ⅲ) chloride with 12-crown-4 in MeCN/MeOH mixed solvent produces an anhydrous complex,LaCl3(12-crown-4)(MeOH)(complex Ⅰ),C9H20O5LaCl3(Mr= 453.6),in which the La(Ⅲ) ion is 8-coordinated by three Cl anions,four oxygen atoms from a crown ligand and a methanol oxygen atom,the complex molecules were connected into a dimer by two O(MeOH)…Cl hydrogen bonds.Reaction of complex Ⅰ with phen(1,10-phenanthroline) gives the crystallization of[LaCl3 (phen)2(H2O)]·MeOH(complex Ⅱ),C25H22O2N4LaCl3(Mr= 655.8) in which the crown ligand is totally replaced by two phen molecules.Cell parameters for the two complexes are a= 9.389(3)[13.228 (5)],b=11.382(4)[10.767(3)],c=7.542(3)[18.520(6) ];α=94.32(3)[90.0],β=102.10(2)[102.01(3)],γ=91. 83(3)[90. 0]°with space group P1[P21/α];V=784.5(5)[2580(1)3,Z=2[4];μ(MoKα)=32.8[20. 2]cm-1;F (000)=444[1296];R=0.042[0.045];Rω=0.044[0.036] for 2398 [2345] observed reflections withⅠ>3σ(Ⅰ).The La(Ⅲ) ion in complex Ⅱ is 8-coordinated by three Cl anions,four N atoms of two phen molecules and one water molecule.The methanolmolecule forms a hydrogen bond with Cl(3) atom.展开更多
ESR and IR measurements have been carried out for a copper(Ⅱ)complex of phenolic polymeric crown ether,As a result,the triplet ESR spectrum(S=1)of 3d_z2 ground state copper(Ⅱ)ions was first observed for the powder s...ESR and IR measurements have been carried out for a copper(Ⅱ)complex of phenolic polymeric crown ether,As a result,the triplet ESR spectrum(S=1)of 3d_z2 ground state copper(Ⅱ)ions was first observed for the powder sample.It indicated that there existed intramolecular spin-spin interaction betweeen 3d_Z2 ground state copper(Ⅱ)and copper(Ⅱ)ions.In this binuclear triplet cluster,the axial ligntion of one water molecule in a sandwich position to two adjacent copper(Ⅱ) ions was also confirmed by IR spectra,All things considered,a possible structure for the complex was proposed.展开更多
The interaction of lanthanum(Ⅲ) chloride with 12-crown-4 in MeCN/MeOH mixed solvent produces an anhydrous complex,LaCl3(12-crown-4)(MeOH)(complex Ⅰ),C9H20O5LaCl3(Mr= 453.6),in which the La(Ⅲ) ion is 8-coordinated b...The interaction of lanthanum(Ⅲ) chloride with 12-crown-4 in MeCN/MeOH mixed solvent produces an anhydrous complex,LaCl3(12-crown-4)(MeOH)(complex Ⅰ),C9H20O5LaCl3(Mr= 453.6),in which the La(Ⅲ) ion is 8-coordinated by three Cl anions,four oxygen atoms from a crown ligand and a methanol oxygen atom,the complex molecules were connected into a dimer by two O(MeOH)…Cl hydrogen bonds.Reaction of complex Ⅰ with phen(1,10-phenanthroline) gives the crystallization of[LaCl3 (phen)2(H2O)]·MeOH(complex Ⅱ),C25H22O2N4LaCl3(Mr= 655.8) in which the crown ligand is totally replaced by two phen molecules.Cell parameters for the two complexes are a= 9.389(3)[13.228 (5)],b=11.382(4)[10.767(3)],c=7.542(3)[18.520(6) ];α=94.32(3)[90.0],β=102.10(2)[102.01(3)],γ=91. 83(3)[90. 0]°with space group P1[P21/α];V=784.5(5)[2580(1)3,Z=2[4];μ(MoKα)=32.8[20. 2]cm-1;F (000)=444[1296];R=0.042[0.045];Rω=0.044[0.036] for 2398 [2345] observed reflections withⅠ】3σ(Ⅰ).The La(Ⅲ) ion in complex Ⅱ is 8-coordinated by three Cl anions,four N atoms of two phen molecules and one water molecule.The methanolmolecule forms a hydrogen bond with Cl(3) atom.展开更多
The novel complex [K(18-C-6)]_2 [Cd(mnt)_2] [18-C-6 = 18-crown-6, mnt =1,2-dicyanoethene-1,2-dithiolate, C_2S_2-(CN)_2^(2-)] was synthesized and characterized by elementalanalysis, IR spectrum and X-ray diffraction an...The novel complex [K(18-C-6)]_2 [Cd(mnt)_2] [18-C-6 = 18-crown-6, mnt =1,2-dicyanoethene-1,2-dithiolate, C_2S_2-(CN)_2^(2-)] was synthesized and characterized by elementalanalysis, IR spectrum and X-ray diffraction analysis. The complex displays two-dimensional networkstructure of [K(18-C-6)] complex segments and [Cd(mnt)_2] complex segment bridged by S-K-S, S-K-Nand N-K-N interactions between adjacent [K(18-C-6)] and [Cd(mnt)_2] units.展开更多
文摘The single crystal of the complex [Sc(NO_3)_3(H_2O)_2]·(15C5) has been prepared in acetonitrile.The new complex has been characterized by elemental analysis,IR spectra,solubility and molar conductance measurements.The structure of the complex is determined by single crystal X-ray diffraction analysis.
文摘A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemical calculation.The calculated results are in good agreement with that obtained in the experiments.Three Cl atoms are on the same side of Ln in LnCl_3·15-C-5 and the crown ring on the other side.forming a complex molecule with coordination number 8.LnCl_3·15-C-5 is easily hygroscopic in air because of its unsaturated coordination,which differs sharply from the stable Ln(NO_3)_3·15-C-5 com- plex of coordination number 11.The HOMO and neighboring occupied MOs are composed of Cl 3p and O2p, and the LUMO and neighboring unoccupied MOs are composed of Ln orbitals.The level structure easily pro- duces Ln3d satellite in XPS caused by L→Ln charge transfer transition.Due to the coordination,the absolute values of the charge are decreased at Ln and O atoms,but increased at Cl atoms,which is in agreement with XPS results.
文摘Three new solid complexes of macrocyclic polyether ligand 2, 2'-dinitro-4, 5, 4', 5'bis-(15- crown-5)-dihenzo disulfide(L) with trivalent rare earth nitrates having composition of RE(NO_3)_3·L ·6H_2O(RE=Ce, Pr, Nd) have been synthesized in acetonitrile. All the isolated complexes have been characterized by elementary analysis, IR and UV spectra, differential thermal and thermogravimetric analysis, X-ray powder diffraction analysis, molar conductance and measurements of solubility in some general solvents.
文摘Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,Bu,m=0.1,n=1,4)have been synthesized in acetonitrile or acetone.All the isolated complexes have been char- acterized by elementary analysis,IR and UV spectra,differential thermal and thermogravimetric analysis,X-ray powder diffraction analysis,molar conductance and measurementa of solubility in some general solventa.It shows that coordination number of the rare earth cation in the complexes of La,Ce,Pr and Nd nitrate is eleven.
文摘The interaction of lanthanum(Ⅲ) chloride with 12-crown-4 in MeCN/MeOH mixed solvent produces an anhydrous complex,LaCl3(12-crown-4)(MeOH)(complex Ⅰ),C9H20O5LaCl3(Mr= 453.6),in which the La(Ⅲ) ion is 8-coordinated by three Cl anions,four oxygen atoms from a crown ligand and a methanol oxygen atom,the complex molecules were connected into a dimer by two O(MeOH)…Cl hydrogen bonds.Reaction of complex Ⅰ with phen(1,10-phenanthroline) gives the crystallization of[LaCl3 (phen)2(H2O)]·MeOH(complex Ⅱ),C25H22O2N4LaCl3(Mr= 655.8) in which the crown ligand is totally replaced by two phen molecules.Cell parameters for the two complexes are a= 9.389(3)[13.228 (5)],b=11.382(4)[10.767(3)],c=7.542(3)[18.520(6) ];α=94.32(3)[90.0],β=102.10(2)[102.01(3)],γ=91. 83(3)[90. 0]°with space group P1[P21/α];V=784.5(5)[2580(1)3,Z=2[4];μ(MoKα)=32.8[20. 2]cm-1;F (000)=444[1296];R=0.042[0.045];Rω=0.044[0.036] for 2398 [2345] observed reflections withⅠ>3σ(Ⅰ).The La(Ⅲ) ion in complex Ⅱ is 8-coordinated by three Cl anions,four N atoms of two phen molecules and one water molecule.The methanolmolecule forms a hydrogen bond with Cl(3) atom.
文摘ESR and IR measurements have been carried out for a copper(Ⅱ)complex of phenolic polymeric crown ether,As a result,the triplet ESR spectrum(S=1)of 3d_z2 ground state copper(Ⅱ)ions was first observed for the powder sample.It indicated that there existed intramolecular spin-spin interaction betweeen 3d_Z2 ground state copper(Ⅱ)and copper(Ⅱ)ions.In this binuclear triplet cluster,the axial ligntion of one water molecule in a sandwich position to two adjacent copper(Ⅱ) ions was also confirmed by IR spectra,All things considered,a possible structure for the complex was proposed.
文摘The interaction of lanthanum(Ⅲ) chloride with 12-crown-4 in MeCN/MeOH mixed solvent produces an anhydrous complex,LaCl3(12-crown-4)(MeOH)(complex Ⅰ),C9H20O5LaCl3(Mr= 453.6),in which the La(Ⅲ) ion is 8-coordinated by three Cl anions,four oxygen atoms from a crown ligand and a methanol oxygen atom,the complex molecules were connected into a dimer by two O(MeOH)…Cl hydrogen bonds.Reaction of complex Ⅰ with phen(1,10-phenanthroline) gives the crystallization of[LaCl3 (phen)2(H2O)]·MeOH(complex Ⅱ),C25H22O2N4LaCl3(Mr= 655.8) in which the crown ligand is totally replaced by two phen molecules.Cell parameters for the two complexes are a= 9.389(3)[13.228 (5)],b=11.382(4)[10.767(3)],c=7.542(3)[18.520(6) ];α=94.32(3)[90.0],β=102.10(2)[102.01(3)],γ=91. 83(3)[90. 0]°with space group P1[P21/α];V=784.5(5)[2580(1)3,Z=2[4];μ(MoKα)=32.8[20. 2]cm-1;F (000)=444[1296];R=0.042[0.045];Rω=0.044[0.036] for 2398 [2345] observed reflections withⅠ】3σ(Ⅰ).The La(Ⅲ) ion in complex Ⅱ is 8-coordinated by three Cl anions,four N atoms of two phen molecules and one water molecule.The methanolmolecule forms a hydrogen bond with Cl(3) atom.
文摘The novel complex [K(18-C-6)]_2 [Cd(mnt)_2] [18-C-6 = 18-crown-6, mnt =1,2-dicyanoethene-1,2-dithiolate, C_2S_2-(CN)_2^(2-)] was synthesized and characterized by elementalanalysis, IR spectrum and X-ray diffraction analysis. The complex displays two-dimensional networkstructure of [K(18-C-6)] complex segments and [Cd(mnt)_2] complex segment bridged by S-K-S, S-K-Nand N-K-N interactions between adjacent [K(18-C-6)] and [Cd(mnt)_2] units.
