In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff...In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff base macrocyclic ligands incorporating the pyridine moiety,and their complexes,were revised,and in 2015 the chemistry of pentaaza macrocycle ligands with rare earth metals was also summarized.Porphyrin and phthalocyanine ligands are not included in this review,which primarily focuses on complexes with Schiff bases and amines without pendant arms or any additional donor other than nitrogen.The synthetic methods,structural characterization,based on single X-ray crystal data,and properties of the lanthanoid complexes,with special attention to magneto-structural correlations,are presented herein.展开更多
A seawater sample was analyzed for its lanthanoids (Ln’s) contents by inductively coupled plasma mass spectrometry (ICP-MS). The analytical procedure included the pre-concentration and partial purification of Ln’s w...A seawater sample was analyzed for its lanthanoids (Ln’s) contents by inductively coupled plasma mass spectrometry (ICP-MS). The analytical procedure included the pre-concentration and partial purification of Ln’s with a chelating resin disk and the employment of the combination of the internal standard and standard addition methods in ICP-MS, which seemed indispensable for the determination of low-level Ln’s by ICP-MS. The recoveries of the Ln’s with the disk were mostly 70% or better with the concentration factor of 200. The measured concentrations of Ln’s were on the order of ng?dm<sup>–</sup>3 or lower and reasonable except that of neodymium and samarium.展开更多
Six novel pentanuclear complexes [Cu 3Ln 2(ClCH 2CO 2) 12 (H 2O) 8]·2H 2O (Ln=La, Pr, Sm, Gd, Dy, or Er) were synthesized by the reaction of chloroacetic acid with Cu and Ln ions in aqueous solutions. ...Six novel pentanuclear complexes [Cu 3Ln 2(ClCH 2CO 2) 12 (H 2O) 8]·2H 2O (Ln=La, Pr, Sm, Gd, Dy, or Er) were synthesized by the reaction of chloroacetic acid with Cu and Ln ions in aqueous solutions. The X ray crystallography established the structure of the Gd complex, which contains a pair of quadruply acetato bridged CuGd dinuclear subunits, and each of them is linked to the central Cu atom by a single acetato bridge. The coordination sphere of each Gd atom is completed by three aqua ligands [Gd-O=0.242 8(5)-0.244 4(4) nm] to form an 8 coordinated distorted square antiprism. The central Cu atom is coordinated by two oxygen atoms from the two bridging acetato groups and two oxygen atoms from the two monodentate acetato groups in a slightly distorted square planar fashion, while each terminal Cu atom is coordinated by the four acetato oxygen atoms at the basal plane and an aqua ligand at the apical position to form a square pyramid. The variable temperature (4 320 K) magnetic susceptibility data of the Gd complex were measured, and fitted to the Curie Weiss law with C =16.38 K cm 3·mol -1 and θ =-1.55 K, indicating very weak antiferromagnetic interaction.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
The interactions of lanthanoid ions with dipalmitoylphosphatidylcholine bilayer were studied by DSC and Raman spectroscopy.The results show that the addition of lanthanoid ions causes a considerable increase of the ge...The interactions of lanthanoid ions with dipalmitoylphosphatidylcholine bilayer were studied by DSC and Raman spectroscopy.The results show that the addition of lanthanoid ions causes a considerable increase of the gel to liquid crystalline transition temperature of phospholipid and a reduction of order of lateral packing and conformation of acyl chains in SUVs.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
Six novel u-oxamido binuclear complexes, namely Cu(oxpn)Ln(L)2(ClO4)3 (Ln: Eu, Gd, Tb, Nd, Ho, Er), where oxpn is N,N'-bis(3-aminopropyl) oxamido, L denotes 5-nitro-1,10-phenanthroline (abbreviated as NO2-phen), h...Six novel u-oxamido binuclear complexes, namely Cu(oxpn)Ln(L)2(ClO4)3 (Ln: Eu, Gd, Tb, Nd, Ho, Er), where oxpn is N,N'-bis(3-aminopropyl) oxamido, L denotes 5-nitro-1,10-phenanthroline (abbreviated as NO2-phen), have been synthesized and characterized. The magnetic susceptibility of complexes Cu(oxpn)Gd(NO2-phen)2(ClO4)3.2H2O was measured over the 4-300 K and the observed data were successfully simulated by equation based on spin Hamil-tonian operator (H = -2JS1.S2), giving the exchange integral J(Cu-Gd)=-1.62 cm-1. This indicates a weak antiferromagnetic interaction between the Cu(Ⅱ) and Gd(Ⅲ) ions.展开更多
The application of tungstophosphoric acid with Wells-Dawson structure and its derivatives has broad prospect due to their strong acidity and oxidisability. There are some isomeric compounds of 2:17 series of tungstoph...The application of tungstophosphoric acid with Wells-Dawson structure and its derivatives has broad prospect due to their strong acidity and oxidisability. There are some isomeric compounds of 2:17 series of tungstophosphates, such as α and β isomers. The β isomer is not stable and is difficult to prepare. So it is rarely reported. This note describes the synthesis and characterization of some new lanthanoid complexes with a formula M<sub>12</sub>H<sub>5</sub> [Ln(β-P<sub>2</sub>W<sub>17</sub>O<sub>61</sub>)<sub>2</sub>·xH<sub>2</sub>O (Ln<sup>3+</sup>=La, Nd, Sm, Eu, Gd, Dy, M=Bu<sub>4</sub>N<sup>+</sup>, x=2;展开更多
Six novel μ-oxamido trinuclear complexes, namely Cu_2(oxap)_2Ln(ClO_4)_3 (Ln: La, Pr, Nd, Gd, Yb, Ho), where oxap is N,N'-bis(2-aminopropyl)oxamido, have been synthesized. The complex Cu_2(oxap)_2Gd(ClO_4)_3 was ...Six novel μ-oxamido trinuclear complexes, namely Cu_2(oxap)_2Ln(ClO_4)_3 (Ln: La, Pr, Nd, Gd, Yb, Ho), where oxap is N,N'-bis(2-aminopropyl)oxamido, have been synthesized. The complex Cu_2(oxap)_2Gd(ClO_4)_3 was characterized with variable temperature magnetic susceptibility (4-300 K). The exchange integrals J (Cu-Gd) and J'(Cu-Cu) were found to be 0.83 cm^(-1) and -1.62 cm^(-1), indi- cating that very weakly ferromagnetic spin-exchange interaction operates between Cu(II) and Gd (III) ions.展开更多
The enantiomers of carboline-based cryptates were successfully resolved by chiral HPLC.These complexes show high configurational stability under harsh conditions and their absolute configuration was determined by comp...The enantiomers of carboline-based cryptates were successfully resolved by chiral HPLC.These complexes show high configurational stability under harsh conditions and their absolute configuration was determined by comparing theoretical and expe rimental electronic circular dichroism spectra.The e nantiopure cryptates exhibit strong circularly polarized luminescence with a maximum dissymmetry factor glum=0.25 for the f-f transition 5 D0→7 F1(λ=594 nm)under visible light excitation atλgx=400 nm.展开更多
基金Xunta de Galicia for his postdoctoral fellowship(ED481B-2022-068)the Fundación Segundo Gil Dávila for her PhD fellowship。
文摘In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff base macrocyclic ligands incorporating the pyridine moiety,and their complexes,were revised,and in 2015 the chemistry of pentaaza macrocycle ligands with rare earth metals was also summarized.Porphyrin and phthalocyanine ligands are not included in this review,which primarily focuses on complexes with Schiff bases and amines without pendant arms or any additional donor other than nitrogen.The synthetic methods,structural characterization,based on single X-ray crystal data,and properties of the lanthanoid complexes,with special attention to magneto-structural correlations,are presented herein.
文摘A seawater sample was analyzed for its lanthanoids (Ln’s) contents by inductively coupled plasma mass spectrometry (ICP-MS). The analytical procedure included the pre-concentration and partial purification of Ln’s with a chelating resin disk and the employment of the combination of the internal standard and standard addition methods in ICP-MS, which seemed indispensable for the determination of low-level Ln’s by ICP-MS. The recoveries of the Ln’s with the disk were mostly 70% or better with the concentration factor of 200. The measured concentrations of Ln’s were on the order of ng?dm<sup>–</sup>3 or lower and reasonable except that of neodymium and samarium.
文摘Six novel pentanuclear complexes [Cu 3Ln 2(ClCH 2CO 2) 12 (H 2O) 8]·2H 2O (Ln=La, Pr, Sm, Gd, Dy, or Er) were synthesized by the reaction of chloroacetic acid with Cu and Ln ions in aqueous solutions. The X ray crystallography established the structure of the Gd complex, which contains a pair of quadruply acetato bridged CuGd dinuclear subunits, and each of them is linked to the central Cu atom by a single acetato bridge. The coordination sphere of each Gd atom is completed by three aqua ligands [Gd-O=0.242 8(5)-0.244 4(4) nm] to form an 8 coordinated distorted square antiprism. The central Cu atom is coordinated by two oxygen atoms from the two bridging acetato groups and two oxygen atoms from the two monodentate acetato groups in a slightly distorted square planar fashion, while each terminal Cu atom is coordinated by the four acetato oxygen atoms at the basal plane and an aqua ligand at the apical position to form a square pyramid. The variable temperature (4 320 K) magnetic susceptibility data of the Gd complex were measured, and fitted to the Curie Weiss law with C =16.38 K cm 3·mol -1 and θ =-1.55 K, indicating very weak antiferromagnetic interaction.
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The interactions of lanthanoid ions with dipalmitoylphosphatidylcholine bilayer were studied by DSC and Raman spectroscopy.The results show that the addition of lanthanoid ions causes a considerable increase of the gel to liquid crystalline transition temperature of phospholipid and a reduction of order of lateral packing and conformation of acyl chains in SUVs.
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.
基金Project supported by the National Natural Science Foundation of China.
文摘Six novel u-oxamido binuclear complexes, namely Cu(oxpn)Ln(L)2(ClO4)3 (Ln: Eu, Gd, Tb, Nd, Ho, Er), where oxpn is N,N'-bis(3-aminopropyl) oxamido, L denotes 5-nitro-1,10-phenanthroline (abbreviated as NO2-phen), have been synthesized and characterized. The magnetic susceptibility of complexes Cu(oxpn)Gd(NO2-phen)2(ClO4)3.2H2O was measured over the 4-300 K and the observed data were successfully simulated by equation based on spin Hamil-tonian operator (H = -2JS1.S2), giving the exchange integral J(Cu-Gd)=-1.62 cm-1. This indicates a weak antiferromagnetic interaction between the Cu(Ⅱ) and Gd(Ⅲ) ions.
文摘The application of tungstophosphoric acid with Wells-Dawson structure and its derivatives has broad prospect due to their strong acidity and oxidisability. There are some isomeric compounds of 2:17 series of tungstophosphates, such as α and β isomers. The β isomer is not stable and is difficult to prepare. So it is rarely reported. This note describes the synthesis and characterization of some new lanthanoid complexes with a formula M<sub>12</sub>H<sub>5</sub> [Ln(β-P<sub>2</sub>W<sub>17</sub>O<sub>61</sub>)<sub>2</sub>·xH<sub>2</sub>O (Ln<sup>3+</sup>=La, Nd, Sm, Eu, Gd, Dy, M=Bu<sub>4</sub>N<sup>+</sup>, x=2;
基金Project supported by the National Natural Science Foundation or China.
文摘Six novel μ-oxamido trinuclear complexes, namely Cu_2(oxap)_2Ln(ClO_4)_3 (Ln: La, Pr, Nd, Gd, Yb, Ho), where oxap is N,N'-bis(2-aminopropyl)oxamido, have been synthesized. The complex Cu_2(oxap)_2Gd(ClO_4)_3 was characterized with variable temperature magnetic susceptibility (4-300 K). The exchange integrals J (Cu-Gd) and J'(Cu-Cu) were found to be 0.83 cm^(-1) and -1.62 cm^(-1), indi- cating that very weakly ferromagnetic spin-exchange interaction operates between Cu(II) and Gd (III) ions.
基金Project supported by the German Research Foundation(DFG,research grant SE1448/7-1 for M.S.)German Academic Scholarship Foundation(Studienstiftung des deutsches Volkes,predoctoral fellowship for E.K.)。
文摘The enantiomers of carboline-based cryptates were successfully resolved by chiral HPLC.These complexes show high configurational stability under harsh conditions and their absolute configuration was determined by comparing theoretical and expe rimental electronic circular dichroism spectra.The e nantiopure cryptates exhibit strong circularly polarized luminescence with a maximum dissymmetry factor glum=0.25 for the f-f transition 5 D0→7 F1(λ=594 nm)under visible light excitation atλgx=400 nm.
文摘目的:探讨消化道铅暴露对大鼠体内铅及其他金属元素含量的影响。方法:将SD大鼠随机分成对照组和不同剂量受试组,采用醋酸铅溶液隔天灌胃染毒,连续染毒5次后收集大鼠全血、尿液与粪便。用电感耦合等离子体质谱仪(inductively coupled plasma mass spectrometry,ICP-MS)和电感耦合等离子体发射光谱仪(inductively coupled plasma atom emission spectrometry,ICP-AES)测定样品中铅及18种金属元素的含量。结果:染毒后大鼠体重及各脏体比组间差异无统计学意义(P>0.05)。血铅含量、尿铅及粪铅总量均随着铅染毒剂量的增加而呈升高趋势,但尿铅总量在高剂量组不再升高。大鼠全血中钠、镁、钾、锶、锑、铊、铋元素含量,尿液中钾、铁、锑含量,粪便中钙、铁、锌、铜、铊、铋及稀土元素含量,组间差异均有统计学意义(P<0.05)。结论:铅可能通过竞争共同转运载体而影响二价金属离子(如钙、镁、铁、锌、铜、锶)的代谢,同时可引起轻稀土元素及有毒元素铊、铋的排出,并改变机体内锑、钠、钾元素水平,但未观察到铅对大鼠体内钼、镉元素的影响。
