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1.
The 1D chain red luminescent europium coordination polymer: {[Eu2L6(DMF)(H2O)] · 2DMF · H2O}n ( I ) (L = 4‐chloro‐cinnamic acid anion, C9H6ClO2, DMF = N, N‐dimethylformamide) was synthesized by the reaction of Eu(OH)3 and 4‐chloro‐cinnamic acid ligand. The structure of the coordination polymer was determined by single‐crystal X‐ray diffraction analysis. It reveals that there exists two crystallographically nonequivalent europium atoms in each unit of this coordination polymer and Eu3+ ions are connected by two alternating bridging modes to form an endless polymer structure. The luminescent properties and energy transfer process in the complex are investigated at room temperature.  相似文献   

2.
The Zintl phase Eu2Si was synthesized from elemental europium and silicon in a sealed tantalum tube in a high‐frequency furnace at 1270 K and subsequent annealing at 970 K. Investigation of the sample by X‐ray powder and single crystal techniques revealed: Co2Si (anti‐PbCl2) type, space group Pnma, a = 783.0(1), b = 504.71(9), c = 937.8(1) pm, wR2 = 0.1193, 459 F2 values and 20 variables. The structure contains two europium and one silicon site. 151Eu Mössbauer spectroscopic data show a single signal at an isomer shift of −9.63(3) mm/s, compatible with divalent europium. Within the Zintl concept electron counting can be written as (2Eu2+)4+Si4−, in agreement with the absence of Si‐Si bonding. Each silicon atom has nine europium neighbors in the form of a tri‐capped trigonal prism. The silicon coordinations of the Zintl phases Eu2Si, Eu5Si3, EuSi, and EuSi2 are compared.  相似文献   

3.
A new mononuclear europium complex incorporating the (+)‐di‐p‐toluoyl‐d ‐tartaric acid (d ‐H2DTTA) ligand, namely, catena‐poly[tris{μ2‐3‐carboxy‐2,3‐bis[(4‐methylphenyl)carbonyloxy]propanoato}tris(methanol)europium(III)], [Eu(C20H17O8)3(CH3OH)3]n, (I), has been synthesized and characterized by IR spectroscopy, elemental analysis, powder X‐ray diffraction and single‐crystal X‐ray diffraction analysis. The structure analysis indicates that complex (I) crystallizes in the trigonal space group R3 and exhibits an infinite one‐dimensional chain structure, in which the Eu3+ ion is surrounded by six O atoms from six d ‐HDTTA? ligands and three O atoms from three coordinated methanol molecules, thus forming a tricapped trigonal prism geometry. The d ‐H2DTTA ligand is partially deprotonated and adopts a μ1,6‐coordination mode via two carboxylate groups to link adjacent Eu3+ ions, affording an infinite one‐dimensional propeller‐shaped coordination polymer chain along the c axis, with an Eu…Eu distance of 7.622 (1) Å. Moreover, C—H…π interactions lead to the formation of helical chains running along the c axis and the whole structure displays a snowflake pattern in the ab plane. The circular dichroism spectrum confirms the chirality of complex (I). The solid‐state photoluminescence properties were also investigated at room temperature and (I) exhibits characteristic red emission bands derived from the Eu3+ ion (CIE 0.63, 0.32), with a reasonably long lifetime of 0.394 ms, indicating effective energy transfer from the ligand to the metal centre. In addition, a magnetic investigation reveals single‐ion magnetic behaviour. The spin‐orbit coupling parameter (λ) between the ground and excited states is fitted to be 360 (2) cm?1 through Zeeman perturbation. Therefore, complex (I) may be regarded as a chiral optical‐magneto bifunctional material.  相似文献   

4.
In this study, a series of Sr(LiAl3)1?x(SiMg3)xN4:Eu2+ (SLA‐SSM) phosphors were synthesized by a solid‐solution process. The emission peak maxima of SLA‐SSM range from 615 nm to 680 nm, which indicates structural differences in these materials. 7Li solid‐state NMR spectroscopy was utilized to distinguish between the Li(1)N4 and Li(2)N4 tetrahedra in SLA‐SSM. Differences in the coordination environments of the two Sr sites were found which explain the unexpected luminescent properties. Three discernible morphologies were detected by scanning electron microscopy. Temperature‐dependent photoluminescence and decay times were used to understand the diverse environments of europium ions in the two strontium sites Sr1 and Sr2, which also support the NMR analysis. Moreover, X‐ray absorption near‐edge structure studies reveal that the Eu2+ concentration in SLA‐SSM is much higher than that in in SrLiAl3N4:Eu2+ and SrSiMg3N4:Eu2+ phosphors. Finally, an overall mechanism was proposed to explain the how the change in photoluminescence is controlled by the size of the coordinated cation.  相似文献   

5.
The cubic inverse Perovskites (Eu3O)In and (Eu3O)Sn were prepared from the metals and Eu2O3 or SnO2, respectively. For (Eu3O)In the crystal structure analysis was performed on single crystal X‐ray diffraction data (space group , a = 512.79(3) pm, Z = 1, Rgt(F) = 0.022, wR(F2) = 0.044). The data indicated full occupancy on all sites and a fully ordered structure. According to magnetic susceptibility measurements and X‐ray absorption spectroscopic data at the Eu LIII edge both compounds contain europium in the 4f7 (Eu2+) electronic state. (Eu3O)In orders ferromagnetically at 185(5) K, (Eu3O)Sn shows antiferromagnetic order at 31.4(2) K. Both compounds behave as metallic conductors in electrical resistivity measurements. However, (Eu3O)In may be classified a metal, while (Eu3O)Sn is more likely a heavily doped degenerated semiconductor or semimetal according to the absolute values of the resistivity.  相似文献   

6.
The new clathrate Ba8–xEuxGe433 (x = 0.6) was synthesized at a pressure of 1 GPa and temperatures of up to 1220 K by means of a multi‐anvil device (Walker module) and a hydraulic 1000 ton press. X‐ray powder diffraction data indicate that the crystal structure of Ba8–xEuxGe433 (x = 0.6, space group , a = 21.2588(3) Å) corresponds to that of Ba8Ge433. Measurements of the magnetic susceptibility of Ba8–xEuxGe433 reveal Curie‐paramagnetic behaviour and prove that the electronic state of europium corresponds to 4f7, i.e., Eu2+. Electrical resistivity shows a metal‐like temperature dependence and ρ(300) ≈ 2mΩ cm for x = 0.6. Heat capacity measurements reveal an upturn of cp/T(T) below 7 K that is attributed to magnetic interaction of the europium ions.  相似文献   

7.
Yellow single crystals of Eu4OI6 were grown from fluxes in Ta ampoules and structurally characterized by X‐ray diffraction. Eu4OI6 crystallizes in a hexagonal system and is isotypic with the corresponding chloride and bromide compounds. The O atom and one Eu atom lie on sites with 3m symmetry; the other Eu atom and the two unique I atoms are at sites with m symmetry. The structure is characterized by O‐centered tetrahedra of divalent europium cations [Eu—O = 2.391 (15) and 2.416 (5) Å, and mean Eu—Eu = 3.94 Å] and hexagonal channels along [001] filled with iodide anions.  相似文献   

8.
New Hexachalcogeno‐Hypodiphosphates of Alkaline‐Earth Metals and Europium Six hexathio‐ and hexaseleno‐hypodiphosphates respectively with the formula M2P2X6 (M = Ca, Sr, Eu, Ba; X = S, Se) were prepared by heating the elements at 750 °C (60 h) and their crystal structures were determined by single crystal X‐ray methods. Eu2P2S6 (a = 9.396(2), b = 7.531(2), c = 6.593(2) Å, β = 91.48(2) °), Ba2P2S6 (a = 9.966(1), b = 7.580(2), c = 6.737(2) Å, β = 91.17(3) °), Ca2P2Se6 (a = 9.664(2), b = 7.519(2), c = 6.859(1) Å, β = 92.02(3) °), Sr2P2Se6 (a = 9.844(2), b = 7.788(2), c = 6.963(1) Å, β = 91.50(3) °), Eu2P2Se6 (a = 9.779(2), b = 7.793(2), c = 6.957(1) Å, β = 91.29(3) °), and Ba2P2Se6 (a = 10.355(2), b = 7.862(2), c = 7.046(1) Å, β = 90.83(3) °) are isotypic and crystallize in the high temperature form of Sn2P2S6 (P21/n; Z = 2). The discrete ethanlike (P2X6)4— anions in staggered conformation are linked via X—M—X bonds to a three‐dimensional structure and in the course of this Ca2+, Sr2+, and Eu2+ are coordinated by 8 and Ba2+ by 8+1 S and Se atoms respectively. Susceptibility measurements of Eu2P2S6 from 2 K to room temperature show Curie‐Weiss behavior with an experimental magnetic moment of 7.43(2) μB/Eu. No magnetic ordering was observed down to 2 K. A 151Eu Mössbauer spectrum at 77 K shows only one signal at an isomer shift of δ = —12.6(1) mm/s. The europium atoms in Eu2P2S6 are therefore in a stable divalent oxidation state.  相似文献   

9.
This study presents a sensitive voltammetric determination of terbutaline (TER) on a platform based on carbon nanotubes (CNTs) and europium oxide nanoparticles (Eu2O3NPs) coated glassy carbon electrodes (GCEs). An ultrasonic bath was performed for the preparation of composite material. The material was characterized by energy dispersive X‐ray spectroscopy (EDX), X‐ray diffraction method (XRD) and scanning electron microscopy (SEM). The Eu2O3NPs/CNTs/GCE system was assessed for the oxidation of terbutaline (TER). A broad oxidation peak was appeared at 0.71 V using a bare GCE. However, the voltammetry of TER has been improved at a GCE coated with CNTs and a well‐defined anodic peak exhibited at 0.61 V. Furthermore, the nanoparticles of Eu2O3 and CNTs coated GCE has greatly improved the electrochemical behaviour of TER and a sharp peak was appeared at 0.59 V. Cyclic voltammetry at Eu2O3NPs/CNTs/GCE also reveals a high catalytic effect for the oxidation of TER with an oxidation peak that is distinctly enhanced compared to GCE and CNTs/GCE. Eu2O3 nanoparticles were utilized to enhance the surface area of GCE and then improve the sensitivity of the procedure. The response of TER was linear over a concentration range of 2.0×10?8 M ?9.5×10?6 M with an LOD of 3.7×10?9 M. Square wave voltammetric analysis of tablets by Eu2O3NPs/CNTs/GCE yielded a recovery of 99.2 % with an RSD% of 3.2. The modified electrode (EuO2NPs/CNTs/GCE) provides accuracy and precision to the analysis of samples.  相似文献   

10.
Highly luminescent, photostable, and soluble lanthanide pentafluorobenzoates have been synthesized and thoroughly characterized, with a focus on EuIII and TbIII complexes as visible emitters and NdIII, ErIII, and YbIII complexes as infrared emitters. Investigation of the crystal structures of the complexes in powder form and as single crystals by using X‐ray diffraction revealed five different structural types, including monomeric, dimeric, and polymeric. The local structure in different solutions was studied by using X‐ray absorption spectroscopy. The photoluminescence quantum yields (PLQYs) of terbium and europium complexes were 39 and 15 %, respectively; the latter value was increased almost twice by using the heterometallic complex [Tb0.5Eu0.5(pfb)3(H2O)] (Hpfb=pentafluorobenzoic acid). Due to the effectively utilized sensitization strategy (pfb)?→Tb→Eu, a pure europium luminescence with a PLQY of 29 % was achieved.  相似文献   

11.
Nitridophosphates MP2N4:Eu2+ (M=Ca, Sr, Ba) and BaSr2P6N12:Eu2+ have been synthesized at elevated pressures and 1100–1300 °C starting from the corresponding azides and P3N5 with EuCl2 as dopant. Addition of NH4Cl as mineralizer allowed for the growth of single crystals. This led to the successful structure elucidation of a highly condensed nitridophosphate from single‐crystal X‐ray diffraction data (CaP2N4:Eu2+ (P63, no. 173), a=16.847(2), c=7.8592(16) Å, V=1931.7(6) Å3, Z=24, 2033 observed reflections, 176 refined parameters, wR2=0.096). Upon excitation by UV light, luminescence due to parity‐allowed 4f6(7F)5d1→4f7(8S7/2) transition was observed in the orange (CaP2N4:Eu2+, λmax=575 nm), green (SrP2N4:Eu2+, λmax=529 nm), and blue regions of the visible spectrum (BaSr2P6N12:Eu2+ and BaP2N4:Eu2+, λmax=450 and 460 nm, respectively). Thus, the emission wavelength decreases with increasing ionic radius of the alkaline‐earth ions. The corresponding full width at half maximum values (2240–2460 cm?1) are comparable to those of other known Eu2+‐doped (oxo)nitrides emitting in the same region of the visible spectrum. Following recently described quaternary Ba3P5N10Br:Eu2+, this investigation represents the first report on the luminescence of Eu2+‐doped ternary nitridophosphates. Similarly to nitridosilicates and related oxonitrides, Eu2+‐doped nitridophosphates may have the potential to be further developed into efficient light‐emitting diode phosphors.  相似文献   

12.
Low‐Temperature Oxidation in Liquid Ammonia: [Eu2(Ind)4(NH3)6], the First Indolate of a Rare Earth Element Intensively yellow to orange coloured, transparent crystals of [Eu2(Ind)4(NH3)6] were obtained by low‐temperature oxidation of europium metal with indole (C8H6NH) in liquid ammonia at —50 °C and subsequent melting of the reaction mixture in excess indole at 120 °C. [Eu2(Ind)4(NH3)6] has a dimeric structure and contains divalent Eu. The coordination sphere around the europium atoms consists of five N atoms of two cisoid indolate anions and three NH3 molecules as well as an η5‐coordinating π‐system of another indolate ligand, bridging to the next Eu atom with an sp2‐orbital.  相似文献   

13.
A new transition‐metal‐containing Zintl phase, Eu10Cd6Bi12, was synthesized by combining the elements in excess molten Cd. Single‐crystal X‐ray diffraction studies indicated that this compound crystallizes in the orthorhombic space group Cmmm (No. 65) with a=7.840(2), b=24.060(7), and c=4.7809(14) Å. The crystal structure of Eu10Cd6Bi12 can be viewed as a stacking of a series of [Cd6Bi12] double layers, which are arranged alternately along the b axial direction. The layers are composed of corner‐ and edge‐shared CdBi4 tetrahedra, a common feature in the crystal chemistry of many transition‐metal Zintl phases. Electronic‐band‐structure calculations confirm the closed‐shell configuration of all constituent elements and corroborate the electron count inferred by the Zintl formalism, that is, [Eu2+]10[Cd2+]6[Bi3?]8[Bi2?]4. Magnetic‐susceptibility measurements confirm the divalency of europium and show the existence of a long‐range antiferromagnetic order of the Eu spins below 12.3 K.  相似文献   

14.
Luminescence properties of divalent europium in the mixed‐anion hydride chloride EuHCl were studied for the first time. Olive‐green single crystals of EuHCl (PbFCl‐type structure: tetragonal, P4/nmm, a = 406.58(3) pm, c = 693.12(5) pm, c/a = 1.705, Z = 2) resulted from the reaction of elemental europium (Eu), sodium hydride (NaH) and sodium chloride (NaCl), while powder samples were prepared from the binary components europium dihydride (EuH2) and dichloride (EuCl2). Low temperature X‐ray powder diffraction proved the absence of phase transitions for 12(2) K ≤ T ≤ 295(2) K. Bright green emission was observed under UV‐excitation and assigned to the 4f65d1–4f7 transition of divalent europium. Temperature‐dependent luminescence absorption and emission, as well as lifetime measurements were carried out on single crystal and powder samples. Surprisingly, only limited concentration quenching was found. Additionally, two emission bands (485 and 510 nm) are observed, whose intensity ratio depends strongly on temperature. In order to explain this behavior for a single Eu2+ site, we suggest either a dynamical Jahn–Teller effect in the excited 5d1 state or emission from both a 4f65d1 state and a trapped exciton state.  相似文献   

15.
The new layered oxonitridosilicate EuSi2O2N2 has been synthesized in a radio‐frequency furnace at temperatures of about 1400 °C starting from europium(III ) oxide (Eu2O3) and silicon diimide (Si(NH)2). The structure of the yellow material has been determined by single‐crystal X‐ray diffraction analysis (space group P1 (no. 1), a=709.5(1), b=724.6(1), c=725.6(1) pm, α=88.69(2), β=84.77(2), γ=75.84(2)°,V=360.19(9)×106 pm3, Z=4, R1=0.0631, 4551 independent reflections, 175 parameters). Its anionic Si2O2N22? layers consist of corner‐sharing SiON3 tetrahedra with threefold connecting nitrogen and terminal oxygen atoms. High‐resolution transmission electron micrographs indicate both ordered and disordered crystallites as well as twinning. Magnetic susceptibility measurements of EuSi2O2N2 exhibit Curie–Weiss behavior above 20 K with an effective magnetic moment of 7.80(5) μB Eu?1, indicating divalent europium. Antiferromagnetic ordering is detected at 4.5(2) K. EuSi2O2N2 shows a field‐induced transition with a critical field of 0.50(5) T. The four crystallographically different europium sites cannot be distinguished by 151Eu Mössbauer spectroscopy. The room‐temperature spectrum is fitted by one signal at an isomer shift of δ=?12.3(1) mm s?1 subject to quadrupole splitting of ΔEQ=?2.3(1) mm s?1 and an asymmetry parameter of 0.46(3). Luminescence measurements show a narrow emission band with regard to the four crystallographic europium sites with an emission maximum at λ=575 nm.  相似文献   

16.
The indides Eu2Pd2In and Eu2Pt2In were synthesized from the elements in sealed tantalum tubes in an induction furnace. The samples were characterized by powder X‐ray diffraction. The structures were refined on the basis of single‐crystal X‐ray diffractometer data: HT‐Pr2Co2Al type, C2/c, a = 1035.7(2), b = 592.9(1), c = 823.6(2) pm, β = 104.26(1) °, wR2 = 0.026, 1075 F2 values, 25 variables for Eu2Pd2In and a = 1017.2(2), b = 588.7(1), c = 826.5(1) pm, β = 103.76(1) °, wR2 = 0.062, 706 F2 values, 25 variables for Eu2Pt2In. The indium atoms have four platinum (palladium) neighbors in strongly distorted tetrahedral coordination at Pt–In and Pd–In distances ranging from 273 to 275 pm. These InPd4/2 and InPt4/2 units are condensed via common edges to infinite InPd2 and InPt2 chains, which are surrounded by the europium atoms. The chains form the motif of hexagonal rod packing.  相似文献   

17.
A novel orange‐yellow‐emitting Ba3Gd(PO4)3:x Eu2+,y Mn2+ phosphor is prepared by high‐temperature solid‐state reaction. The crystal structure of Ba3Gd(PO4)3:0.005 Eu2+,0.04 Mn2+ is determined by Rietveld refinement analysis on powder X‐ray diffraction data, which shows that the cations are disordered on a single crystallographic site and the oxygen atoms are distributed over two partially occupied sites. The photoluminescence excitation spectra show that the developed phosphor has an efficient broad absorption band ranging from 230 to 420 nm, perfectly matching the characteristic emission of UV‐light emitting diode (LED) chips. The emission spectra show that the obtained phosphors possess tunable color emissions from yellowish‐green through yellow and ultimately to reddish‐orange by simply adjusting the Mn2+ content (y) in Ba3Gd(PO4)3:0.005 Eu2+,y Mn2+ host. The tunable color emissions origin from the change in intensity between the 4f–5d transitions in the Eu2+ ions and the 4T16A1 transitions of the Mn2+ ions through the energy transfer from the Eu2+ to the Mn2+ ions. In addition, the mechanism of the energy transfer between the Eu2+ and Mn2+ ions are also studied in terms of the Inokuti–Hirayama theoretical model. The present results indicate that this novel orange‐yellow‐emitting phosphor can be used as a potential candidate for the application in white LEDs.  相似文献   

18.
A mixed‐valence Mn complex {[MnIIMnIII(HL)2(4,4′‐bpy)(H2O)2] · (ClO4)(DMF)3(4,4′‐bpy)0.5}n ( 1 ) [H2L = 3‐(2‐phenol)‐5‐(pyridin‐2‐yl)‐1,2,4‐triazole] was synthesized and characterized by X‐ray single‐crystal structure analysis and magnetic susceptibility. Single‐crystal X‐ray analysis revealed that complex 1 has a dinuclear core, in which adjacent central MnIII atoms are linked by 4,4′‐bipyridine to form an infinite one‐dimensional (1D) molecular configuration. According to the Mn surrounding bond lengths and bond valence sum (BVS) calculations, we demonstrated that the Mn atom coordinated to the pyridine N atoms is in the +2 oxidation state, while another Mn atom coordinated to the phenolic oxygen atoms is in the +3 oxidation state. Magnetic susceptibility data of the complex 1 indicate that the ferromagnetic interaction dominates in this complex.  相似文献   

19.
To reveal the surface elemental composition and chemical states of the Ce1 ? x Eux CrO3 nano‐powders (x= 0.0, 0.3, 0.5, 0.7, 0.8, 1.0), X‐ray photoelectron spectroscopy was carried out in two conditions of before and after surface cleaning. This surface characterization described the core level binding energies of cerium, europium and chromium with different oxidation states. These results verified the morphology of the particles' surface which can be a confirmation of the spin disorder in these core‐shell structures. The effect of surface Ar sputtering on the oxidation states were studied. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

20.
Optical spectra (powder reflectance, UV/Vis/NIR region), and temperature dependent magnetic behavior (χ, μ/μB) were recorded for the series of anhydrous europium(III) phosphates EuIII3O3(PO4), EuIIIPO4, EuIII2P4O13, lt- and ht-EuIII(PO3)3, and EuIIIP5O14. By modeling within the AOM framework, the experimental data can be related to the ligand-field splitting experienced by the Eu3+ ions in the various mainly low-symmetry coordination environments. Our study confirms the well-established relation eσ(Eu3+–O2–) ~ d(Eu3+–O2–)–7.0 between the AOM parameter and the interatomic distance. In addition it is shown that eσ(Eu3+–O2–) depends strongly on the highly variable polarizability of the oxygen ligator atoms. This polarizability can be related to the optical basicity Λ of the various phosphates.  相似文献   

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