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
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
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
A series of hybrid organo-inorganic mononuclear lanthanoid complexes,[n-NBu_(4)]_(3)[LnH(PW_(11)O_(39))(phen)_(2)]·H_(2)O,denoted as LM^(4)-1-Ln(Ln=Dy^(Ⅲ),Tb^(Ⅲ),Eu^(Ⅲ),Nd^(Ⅲ),Er^(Ⅲ),Ho^(Ⅲ) and Gd^(Ⅲ)),wer...A series of hybrid organo-inorganic mononuclear lanthanoid complexes,[n-NBu_(4)]_(3)[LnH(PW_(11)O_(39))(phen)_(2)]·H_(2)O,denoted as LM^(4)-1-Ln(Ln=Dy^(Ⅲ),Tb^(Ⅲ),Eu^(Ⅲ),Nd^(Ⅲ),Er^(Ⅲ),Ho^(Ⅲ) and Gd^(Ⅲ)),were synthesized via hydrothermal synthesis and were structurally characterized by X-ray diffraction.The optical properties of all complexes have been investigated in the solid state.The temperature-dependent emission spectra of LM^(4)-1-Dy,LM^(4)-1-Tb and LM^(4)-1-Eu complexes show intense lanthanoid emissions in the visible region,while LM^(4)-1-Nd shows near-infrared(NIR)luminescence.The Eu^(Ⅲ) complex shows typical strong red emissions from the ^(5)D_(0)→^(7)F_(0,1,2,3,4) transitions,with the CIE colour coordinates(0.631,0.364),the colour purity value of 83.9% and a quantum yield of up to 4.3%,suggesting that the organic fragment has an effect on the optical properties compared to fully inorganic systems,making this complex very attractive as a red component of light-emitting diodes.The luminescence decays of LM^(4)-1-Dy,LM^(4)-1-Tb and LM^(4)-1-Eu exhibit a biexponential behaviour,with τ_(AV)=4.1(7)μs,0.35(2)ms and 0.94(3)ms,respectively.The values obtained for Judd-Ofelt intensity parameters Ω_(2) and Ω_(4) support the interaction between the Eu^(Ⅲ) and the ligands.Furthermore,those with Er^(Ⅲ) and Ho^(Ⅲ) present weak emissions in the visible region.The T-dependent photoluminescence results show that the LM^(4)-1-Dy,LM^(4)-1-Tb and LM^(4)-1-Nd complexes have good temperature sensitivity,demonstrating that the materials have the potential to be used as a sensing element for luminescent thermometers in different temperature ranges.展开更多
Two P^(Ⅲ)–Sb^(Ⅲ)-heteroatom-templated lanthanoid(Ln)-inserted polyoxotungstates[H_(2)N(CH_(3))_(2)]_(10)NaH_(9)[Ln_(4)(H_(2)O)_(14)W_(7)O_(15)(H_(2)MA)_(4)][Sb^(Ⅲ)W_(9)O_(33)]_(2)[HP^(Ⅲ)Sb^(Ⅲ)W_(15)O_(54)]_(2)&#...Two P^(Ⅲ)–Sb^(Ⅲ)-heteroatom-templated lanthanoid(Ln)-inserted polyoxotungstates[H_(2)N(CH_(3))_(2)]_(10)NaH_(9)[Ln_(4)(H_(2)O)_(14)W_(7)O_(15)(H_(2)MA)_(4)][Sb^(Ⅲ)W_(9)O_(33)]_(2)[HP^(Ⅲ)Sb^(Ⅲ)W_(15)O_(54)]_(2)·44H_(2)O[Ln=Nd^(3+)(1),Pr^(3+)(2)]embellished with DL-malic acid(H_(3)MA)ligand were achieved for the first time.The[Ln_(4)(H_(2)O)_(14)W_(7)O_(15)(H_(2)MA)_(4)][Sb^(Ⅲ)W_(9)O_(33)]_(2)[HP^(Ⅲ)Sb^(Ⅲ)W_(15)O_(54)]_(2)^(20−)polyanion is assembled from two trivacant Keggin[B-α-Sb^(Ⅲ)W_(9)O_(33)]^(9)−and two trivacant Dawson P^(Ⅲ)–Sb^(Ⅲ)-inserted[HP^(Ⅲ)Sb^(Ⅲ)W_(15)O_(54)]11−moieties linked via a central[Ln_(4)(H_(2)O)_(14)W_(7)O_(15)(H_(2)MA)_(4)]^(20+)hybrid cluster.Moreover,adjacent polyanions are connected by Ln–O–W linkers,thus affording an intriguing 1-D structure.The 1@PPY(PPY=polypyrrole)conductive film was fabricated by the electrodeposition of 1 and pyrrole.By virtue of 1@PPY film modified glassy carbon electrode as the electrochemical immunosensor,electrochemical detection of auximone(herein indole-3-acetic acid)was realized.This research pioneers the preparation of P^(Ⅲ)–Sb^(Ⅲ)-heteroatomtemplated Ln-inserted polyoxotungstates and develops the application of POM-based materials for detecting auximone in botany.展开更多
Homogeneous surface deposition of molecules over a large area of the substrate is difficult to achieve but extremely important for proposed applications of magnetic molecules in data storage,information processing or ...Homogeneous surface deposition of molecules over a large area of the substrate is difficult to achieve but extremely important for proposed applications of magnetic molecules in data storage,information processing or molecular spintronics.In this paper we report a simple method for large area surface functionalization with the aim of grafting complex molecules in an organized manner.A proof of concept is given by grafting the complexes[Ln_(2)(SYML)_(3)(H_(2)O)](1 Ln=Eu(Ⅲ),2 Ln=Dy(Ⅲ))on the functionalized Si(100)and using a combination of techniques,including luminescence to track the process.We obtain a homogenous coverage of Si(100)wafers(from 0.5 cm×0.5 cm to 1 cm×1 cm)with complexes 1 and 2.Time of flight secondary ion mass spectroscopy(ToF-SIMS)confirms the presence of the expected mole-cular fragments on the surface.Grazing incidence X-Ray diffraction(GIXRD)measurements show pre-ferred orientations and ordered domains of the molecules.The magnetic properties and anisotropy of the monolayer of grafted molecules are examined by X-Ray magnetic circular dichroism(XMCD),showing a fraction of molecules with a preferred orientation of their easy axis of magnetization at 30°with respect to the surface-normal.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
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.
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FONDECYT 11160830 for financial supportthe REDI170277 project for financial support+7 种基金the partial support from Financiamiento Basal AFB180001(CEDENNA)the LIA-M3-1027 CNRS Collaborative Programfunded by the Spanish MICINN(Unidad de Excelencia“María de Maeztu”MDM-2015-0538 and project CTQ2017-89528-P)the Generalitat Valenciana(PROMETEU/2019/066)MICINN for a Ramón y Cajal contractfinanced in part by the Coordenacão de Aperfeicoamento de Pessoal de Nível Superior(CAPES)-Conselho Nacional de Desenvolvimento Científico e Tecnológico(CNPq)Fundacão de Amparoà Pesquisa do Estado de Goiás(FAPEG)Financiadora de Estudos e Projetos(FINEP)Brazilian agencies.
文摘A series of hybrid organo-inorganic mononuclear lanthanoid complexes,[n-NBu_(4)]_(3)[LnH(PW_(11)O_(39))(phen)_(2)]·H_(2)O,denoted as LM^(4)-1-Ln(Ln=Dy^(Ⅲ),Tb^(Ⅲ),Eu^(Ⅲ),Nd^(Ⅲ),Er^(Ⅲ),Ho^(Ⅲ) and Gd^(Ⅲ)),were synthesized via hydrothermal synthesis and were structurally characterized by X-ray diffraction.The optical properties of all complexes have been investigated in the solid state.The temperature-dependent emission spectra of LM^(4)-1-Dy,LM^(4)-1-Tb and LM^(4)-1-Eu complexes show intense lanthanoid emissions in the visible region,while LM^(4)-1-Nd shows near-infrared(NIR)luminescence.The Eu^(Ⅲ) complex shows typical strong red emissions from the ^(5)D_(0)→^(7)F_(0,1,2,3,4) transitions,with the CIE colour coordinates(0.631,0.364),the colour purity value of 83.9% and a quantum yield of up to 4.3%,suggesting that the organic fragment has an effect on the optical properties compared to fully inorganic systems,making this complex very attractive as a red component of light-emitting diodes.The luminescence decays of LM^(4)-1-Dy,LM^(4)-1-Tb and LM^(4)-1-Eu exhibit a biexponential behaviour,with τ_(AV)=4.1(7)μs,0.35(2)ms and 0.94(3)ms,respectively.The values obtained for Judd-Ofelt intensity parameters Ω_(2) and Ω_(4) support the interaction between the Eu^(Ⅲ) and the ligands.Furthermore,those with Er^(Ⅲ) and Ho^(Ⅲ) present weak emissions in the visible region.The T-dependent photoluminescence results show that the LM^(4)-1-Dy,LM^(4)-1-Tb and LM^(4)-1-Nd complexes have good temperature sensitivity,demonstrating that the materials have the potential to be used as a sensing element for luminescent thermometers in different temperature ranges.
基金supported by the National Natural Science Foundation of China(21871077,21671054,21771052,22071042,22171070)the Program for Innovation Teams in Science and Technology in Universities of Henan Province(20IRTSTHN004)+1 种基金Henan Province Science and Technology Project(182102310815)the Program of First-Class Discipline Cultivation Project of Henan University(2019YLZDYJ02,CJ1205A0240019).
文摘Two P^(Ⅲ)–Sb^(Ⅲ)-heteroatom-templated lanthanoid(Ln)-inserted polyoxotungstates[H_(2)N(CH_(3))_(2)]_(10)NaH_(9)[Ln_(4)(H_(2)O)_(14)W_(7)O_(15)(H_(2)MA)_(4)][Sb^(Ⅲ)W_(9)O_(33)]_(2)[HP^(Ⅲ)Sb^(Ⅲ)W_(15)O_(54)]_(2)·44H_(2)O[Ln=Nd^(3+)(1),Pr^(3+)(2)]embellished with DL-malic acid(H_(3)MA)ligand were achieved for the first time.The[Ln_(4)(H_(2)O)_(14)W_(7)O_(15)(H_(2)MA)_(4)][Sb^(Ⅲ)W_(9)O_(33)]_(2)[HP^(Ⅲ)Sb^(Ⅲ)W_(15)O_(54)]_(2)^(20−)polyanion is assembled from two trivacant Keggin[B-α-Sb^(Ⅲ)W_(9)O_(33)]^(9)−and two trivacant Dawson P^(Ⅲ)–Sb^(Ⅲ)-inserted[HP^(Ⅲ)Sb^(Ⅲ)W_(15)O_(54)]11−moieties linked via a central[Ln_(4)(H_(2)O)_(14)W_(7)O_(15)(H_(2)MA)_(4)]^(20+)hybrid cluster.Moreover,adjacent polyanions are connected by Ln–O–W linkers,thus affording an intriguing 1-D structure.The 1@PPY(PPY=polypyrrole)conductive film was fabricated by the electrodeposition of 1 and pyrrole.By virtue of 1@PPY film modified glassy carbon electrode as the electrochemical immunosensor,electrochemical detection of auximone(herein indole-3-acetic acid)was realized.This research pioneers the preparation of P^(Ⅲ)–Sb^(Ⅲ)-heteroatomtemplated Ln-inserted polyoxotungstates and develops the application of POM-based materials for detecting auximone in botany.
基金support from the Spanish Government Ministerio de Ciencia Innovación y Universidades(project PGC2018-098630-B-I00 and PhD fellowship FPI PRE2019-087801 to GGR)support from CSIC and Ministerio de Ciencia,Innovación y Universidades(projects 201060E013 and 202160E030)+2 种基金support from the Spanish Government Ministerio de Ciencia Innovación y Universidades(PGC2018-093863-B-C21 and MDM-2017-0767)support from the Gobierno de Aragón(project RASMIA E12-20R).ECS,GG,and EB acknowledge beamtime use at ALBA BOREAS(project 2021075217)ESRF SpLine(project 25-02-964).
文摘Homogeneous surface deposition of molecules over a large area of the substrate is difficult to achieve but extremely important for proposed applications of magnetic molecules in data storage,information processing or molecular spintronics.In this paper we report a simple method for large area surface functionalization with the aim of grafting complex molecules in an organized manner.A proof of concept is given by grafting the complexes[Ln_(2)(SYML)_(3)(H_(2)O)](1 Ln=Eu(Ⅲ),2 Ln=Dy(Ⅲ))on the functionalized Si(100)and using a combination of techniques,including luminescence to track the process.We obtain a homogenous coverage of Si(100)wafers(from 0.5 cm×0.5 cm to 1 cm×1 cm)with complexes 1 and 2.Time of flight secondary ion mass spectroscopy(ToF-SIMS)confirms the presence of the expected mole-cular fragments on the surface.Grazing incidence X-Ray diffraction(GIXRD)measurements show pre-ferred orientations and ordered domains of the molecules.The magnetic properties and anisotropy of the monolayer of grafted molecules are examined by X-Ray magnetic circular dichroism(XMCD),showing a fraction of molecules with a preferred orientation of their easy axis of magnetization at 30°with respect to the surface-normal.
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.
