Synthesis and luminescence properties of rare earth ternary complexes consisting of Tb(III), β-diketones and 1,10-phenanthroline (phen)

In order to study the luminescent properties of ternary rare earth complexes with β-diketone ligand, three new β-diketone ligands, 1-phenyl-3-(p-phenylethynylphenyl)-1,3-propanedione(HPPP), 1-(2-thienyl)-3-(p-phenylethynylphenyl)-1,3-propanedione (HTPP) and 1-(2-furyl)-3-(p-phenylethynylphenyl)-1,3-propanedione (HFPP), were synthesized by Sonogashira coupling reaction and Claisen condensation. Three new ternary rare earth complexes, TbL₃phen (L = PPP, TPP, or FPP), were synthesized by the reaction of rare earth chloride TbCl₃,1,10-phenanthroline (phen) with HPPP, HTPP, or HFPP respectively, in alcohol solution. The compositions were characterized by means of elemental analysis, chemical analysis, and IR spectra. Luminescent properties of the three new complexes have been studied. The results show that the ternary Tb(III) complexes only emit the weak fluorescence of the Tb(III) ion, which reveals the triplet state energy of the ligands does not match well with the excited state vibrating energy of Tb³⁺ ion.     

Synthesis and fluorescent properties of europium–polymer complexes containing 1,10-phenanthroline

In this paper, 5-acrylamido-1,10-phenanthroline (AP) was synthesized, then the luminescence material containing Eu–polymer complexes were obtained by two methods. The polymer structure and properties were characterized by FT-IR, UV, fluorescence spectra, DSC, GPC, ICP and XRD. Compared with the two methods the rare earth ions-containing polymers, we obtained copolymer B by the second one that had high and stable fluorescence intensity with the Eu content 0.31%. Comparing the two results via different methods, we have set down the useful basement for the study of the luminescence material containing Eu–polymer complexes.     

Synthesis, crystal structure and properties of two ternary rare earth complexes with aromatic acid and 1,10-phenanthroline

Two dimeric rare-earth complexes [Eu(o-MOBA)₃phen]₂·2H₂O (1), [Tb(o-MOBA)₃phen]₂·2H₂O (2), (where o-MOBA = o-methoxybenzoate, phen = 1,10-phenanthroline) were synthesized and structurally characterized. Both of them consist of neutral dimeric molecules, crystallize in triclinic system, space group P. Each RE(III) ion is nine-coordinated with one 1,10-phenanthroline molecule, one bidentate chelating carboxylate group, two bidentate bridging carboxylate groups and two tridentate bridging carboxylate groups. Complex 1 shows bright red luminescence, 2 shows green luminescence under UV light at room temperature, respectively. The thermal analysis indicates that they are all quite stable to heat.     

EffectofEr~(3+) and Nd~(3+)doping on the luminescent properties of BaMgAl_(10)O_(17):Euphosphor

BaMgAl10O17:Eu blue phosphors were synthesized and the effect of doping er3+ and Nd3+ ions in the phosphor on the luminescent properties was investigated. When the content of Er3+ and Nd3+ ions is small, the phosphor remains single phase and the luminescent intensity of Eu2+ increases effectively. When Er3+ is doped, the shape of the excitation spectrum of the phosphor in the UV (ultraviolet) region remains unchanged. As Nd3+ is doped in the phosphor, the location and intensity of the two excitation peaks, and the emission intensity ratio excited by corresponding UV change dramatically owing to the alternation of crystal field splitting and level barycenter of 4f65d configuration of Eu2+ ion.     

Synthesis, luminescence and quantum yields of Eu(III) mixed complexes with 4,4,4-trifluoro-1-phenyl-1,3-butanedione and 1,10-phenanthroline-N-oxide

The new complex tris(4,4,4-trifluoro-1-phenyl-1,3-butanedionate)(1,10-phenanthroline-N-oxide)europium(III) has been synthesized, characterized, and its photophysical properties (excitation and luminescence spectra, and quantum yields) investigated down to 4.2 K. A similar complex containing H₂O instead of phenNO molecules was also investigated for comparison. The more pronounced temperature dependence of the quantum yield q and the larger difference between the q values upon ligand and direct Eu³⁺ excitation for the hydrated compound show that there are other quenching processes operative, besides the expected multiphonon relaxation via the H₂O vibrations. The results clearly show that the substitution of the water molecules by phenNO leads to greatly enhanced quantum yields (i.e. 30% vs. 66%, upon ligand excitation at 300 K) and longer ⁵D₀ lifetimes (380 μs vs. 670 μs respectively). This can be ascribed to a more efficient ligand-to-metal energy transfer and to less efficient non-radiative ⁵D₀ relaxation processes.     

Eu/Tb共掺杂Y2O3荧光粉的发光性质研究

稀土掺杂荧光粉在固态照明中有良好的应用前景。这里用固相法合成了Y2O3:Eu3 ,Tb3 ,材料结构用X-射线衍射仪进行了表征,发现合成了纯相的Y2O3,掺杂的稀土离子未对基质结构产生影响。稀土离子单掺杂的Y2O3荧光粉在各自特征领域表现出良好的发光性质Y2O3:Tb3 发射出亮绿光,而Y2O3:Eu3 发射出亮红光颜色。调控它们的浓度,可以在Y2O3:0.2% Eu3 , 2%Tb3 处实现白光,详细分析了它们的发光光谱,计算了它们的色坐标,对应的CIE色坐标分别标记在色坐标图中。     

Synthesis,luminescent properties,and theoretical study of novel Sm~(3+) and Dy~(3+) complexes containing β-diketone and 1,10-phenanthroline

Two new ternary complexes of 1-(2-thienyl)-3-(p-phenylethynylphenyl)-1,3-propanedione (HTPP) and 1,10-phenanthroline (phen) with Sm³⁺ and Dy³⁺ were synthesized. The composition of the ternary complexes was characterized as Sm(TPP)₃phen and Dy(TPP)₃phen, respectively, by infrared (IR) spectra, chemical analysis, elemental analysis, and thermodynamic analysis. At room temperature, under UV light excitation, the Sm³⁺ and Dy³⁺ complexes exhibit characteristic emissions of the central ions. It is found that the fluorescence intensity of Sm(TPP)₃phen is stronger than that of Dy(TPP)₃phen. In order to explain this phenomenon, an accurate quantum chemistry calculation was carried out, and the result is in good agreement with the experiment data.     

稀土Gd3+掺杂对钴铁氧体结构与吸波性能的影响

以十六烷基三甲基溴化铵(CTAB)为表面活性剂,C_4H_6CoO_4·6H_2O和FeCl_3·6H_2O为原料,晶化温度180℃,晶化时间8 h,在pH=11的条件下采用水热法制备钴铁氧体纳米颗粒。探究了稀土元素Gd~(3+)的掺杂量对纳米钴铁氧体微观结构与吸波性能的影响。利用X射线衍射(XRD)仪、红外光谱(FT-IR)、透射电镜(TEM)和矢量网络分析(VNA)仪对制备的复合钴铁氧体结构性能进行表征。结果表明,稀土元素Gd~(3+)会对钴铁氧体的晶粒尺寸、形貌和吸波性能产生较大影响。当稀土元素Gd~(3+)掺杂量x≤0.025时,复合钴铁氧体晶粒尺寸随着掺杂量增加在逐渐减小,晶格常数逐渐增加,颗粒的形状变为不规则四边形。当稀土元素Gd~(3+)掺杂量x0.025时,由于稀土元素Gd~(3+)在钴铁氧体中固溶度达到限值,会产生Gd(OH)_3杂质,使钴铁氧体晶粒尺寸变大。当稀土元素Gd~(3+)的掺杂量x=0.025时,所制备的钴铁氧体介电损耗与磁滞损耗增强,吸波反射率达到最小,为-14.9 dB。     

Syntheses, characteristics and fluorescence properties of complexes of terbium with benzoic acid and its derivatives

The binary complexes of terbium with benzoic acid and its derivatives (phthalic acid, iso-phthalic acid, oaminobenzoic acid, salicylic acid, sulfosalicylic acid) were synthesized and their compositions were identified by elemental analyses. UV, IR of the complexes were investigated. The UV spectra indicate that the complexes‘ ultraviolet absorption is mainly the ligands‘ absorption, but the location of peak drifts. The IR spectra show that the IR spectra of complexes are different from those of free ligands, and the band at 400 - 500 cm^-1 , due to the stretching vibration of Tb--O, is absent for free ligands. The fluorescence properties were investigated by using luminescence spectroscope, the results show that all the six complexes of terbium exhibit excellent luminescence, due to the transition from the lowest excited state ^5D4 to ^7F ground state manifold, the complexes of terbium with sulfosalicylic acid have the strongest fluorescence intensity, and is stronger than o-aminobenzoic acid-terbium, whose fluorescence intensity is regarded as the strongest one in the literature, and even stronger than some phosphor of terbium.     

Influence of La^3＋ and Dy^3＋ on the properties of the long afterglow phosphor CaAl2O4： Eu^2＋, Nd^3＋

The long afterglow phosphor CaAl2O4:Eu2+,Nd3+ was prepared by the high temperature solid-state reaction method,and the influence of La3+ and Dy3+ on the properties of the long afterglow phosphor was studied by X-ray diffraction (XRD),photoluminescence (PL),and thermoluminescence (TL),The XRD pattern shows the host phase of CaAl2O4 is produced and no impurity phase appears.The peak wavelength of the phosphor does not vary with La3+ and Dy3+ doping.It implies that the crystal field,which affects the 5d electron states of Eu2+ is not changed dramatically after doping of La3+ and Dy3+.The TL spectra indicate that the phosphor doped with La3+ or Dy3+ produces different depths of trap energy level.In the mechanism of long afterglow luminescence,it is considered that La3+ or Dy3+ works as trap energy level.The decay time lies on the number of electrons in the trap energy level and the rate of the electrons returning to the excitation level.     

Upconversion luminescence properties of Er<Superscript>3+</Superscript> doped GeS<Subscript>2</Subscript>-Ga<Subscript>2</Subscript>S<Subscript>3</Subscript>-KCl chalcohalide glasses

Er3+ ions doped chalcohalide glasses with the composition of 56GeS2-24Ga2S3-20KCl were fabricated by a melt-quenching method.Under 800 nm laser excitation,strong green emissions centered at 525 nm and 550 nm and weak red emission centered at 660 nm were observed,which were assigned to 2H11/2→4I15/2,4S3/2→4I15/2,and 4F9/2→4I15/2 transitions,respectively.The intensity reached maximum when the Er3+ ions concentration was 0.1 mol%.The possible upconversion luminescence mechanism was proposed from the discussion...     

Microstructure and microwave electromagnetic properties of Dy~（3＋）-doped W-type hexaferrites

Ba 1 x Dy x Co 2 Fe 16 O 27 (x = 0.00, 0.05, 0.10, 0.15, and 0.20) was prepared by the solid-state method. The phase structure was studied using powder X-ray diffraction (XRD), the electromagnetic properties were measured, and the reflection loss of Dy 3+ -doped ferrite material was calculated using electromagnetic parameters by the transmission line theory. All XRD patterns showed the single phase of the magnetoplumbite barium ferrite without other intermediate phase when x ≤ 0.15. The values of ε′ and ε″ increased slightly with Dy 3+ ions doping. The values of μ″ and μ′ were improved with Dy 3+ doping, exhibiting excellent microwave magnetic performance. The reasons have also been discussed using the electromagnetic theory. Dy substitution could increase microwave-absorbing performance and broaden frequency band (reflection loss (RL) < -10 dB), and the absorbing peak shifted to high-frequency position. When x = 0.2, ferrite layer exhibited the most excellent microwave-absorbing performance at a thin matching thickness of 1.5 mm. The peak value of RL was around -15 dB, and the frequency band (RL < -10 dB) was about 7 GHz (from 8 to 15 GHz).     

Mechanical behaviors of alumina ceramics doped with rare-earth oxides

The effects of three types of additives Y₂O₃, La₂O₃, and Sm₂O₃ on the sintering and mechanical behaviors of alumina ceramics were investigated. The bending strengths of alumina ceramics with Sm₂O₃ and Y₂O₃ additions were 455 and 439 MPa, respectively, higher than that with La₂O₃ addition. The fracture toughness of the ceramics with Sm₂O₃ and Y₂O₃ were also higher than that with La₂O₃ addition. The fracture mode of rare earth oxides doped alumina ceramics exhibited obvious transgranular fractures as well as intergranular fracture. The results of research show that the improvement of bending strength and fracture toughness of alumina ceramics with rare earth oxides was achieved by refining the grain size and strengthening the grain boundary.     

Synthesis and near-infrared luminescent properties of some ruthenium complexes

A series of seven ruthenium complexes with different ligands were synthesized and their optical, electrochemical and photoluminescent properties were characterized. Electroluminescent properties of these complexes were further evaluated using a light-emitting electrochemical cell with a configuration of indium tin oxide (ITO)/complex (100 nm)/Au (100 nm). Tunable photoluminescence (PL) and electroluminescence (EL) from 630 to 1040 nm have been achieved by adjusting the LUMO and HOMO levels of ruthenium complexes.     

两种黄绿光铱配合物的合成及光物理性质研究

以2-苯基-6-(三氟甲基)-苯并噻唑和5,7-二氟-2-苯基苯并噻唑为主配体,分别与辅助配体三苯基膦合成了两种新型的环金属铱配合物(Ir1和Ir2)。用核磁共振氢谱(¹H-NMR)和质谱(MS)进行表征并确认其结构。用紫外吸收光谱以及荧光发射光谱研究了它们的光物理性质,Ir1和Ir2的最大发射波长分别为548和546 nm,发黄绿光,相对量子产率为41.1%和69.2%,荧光寿命分别为0.65和0.66 μs。密度泛函理论(DFT)计算表明紫外最大吸收峰和荧光发射峰均归因于MLCT/ILCT跃迁。     

Crystal structure and properties of terbium o-methylbenzoate complex with 1,10-phenanthroline [Tb（o-CH3C6H4COO）3（C12H8N2）]2

A terbium o-methylbenzoate complex with 1,10-phenanthroline, Tb(o-MBA)_3phen (where o-MBA =o-methylbenzoate and phen = 1,10-phenanthroline) was prepared from ethanol solution and its crystal structure was deter-mined by X-ray diffraction. The crystal of the complex Tb(o-MBA)_3phen belongs to triclinic crystal system and P 1 (#2)space group. The crystal data are as follows: a=1.4371(4)nm, b=1.7387(2)nm, c=1.3109(2)nm, α=96.37(1)°,β=107.21(2)°, γ=82.78(2)°, V=3.094(1)nm~3, Z=2, M_r=1489.12, D_c=1.598g·cm, μ=2.330mm~(-1) and F(000)=1488.00.The final R and R_w are 0.038 and 0.047 for 8668Π>2σ(Ⅰ)] unique reflections, respectively. In the complex each Tb~(3 ) ion iseight-coordinated by one 1,10-phenanthroline molecule, one bidentate carboxytate group and four bridging carboxylategroups. The carboxylate groups are bonded to the terbium ion in two modes: the chelating bidentate and the bridging biden-tate. Excitation and luminescence data observed at room temperature show that the title complex emits     

Syntheses, characteristics, and fluorescence properties of complexes of europium with benzoic acid and its derivatives

The binary complexes of europium with benzoic acid and its derivatives (phthalic acid, m-phthalic acid,o-aminobenzoic acid, salicylic acid, and sulfosalicylic acid) were synthesized and their compositions were identified by elemental analyses. UV and IR of the complexes have been investigated. The UV spectra indicated that the complexes‘ ultraviolet absorption were mainly the ligands‘ absorption. The IR spectra showed that the IR spectra of complexes are different from those of free ligands. The fluorescence properties of them were investigated by using luminescence spectroscopy, the results showed that only three complexes appear as better luminescence, they were Eu-benzoic acid,Eu-m-phthalic acid and Eu-phthalic acid, while the others exhibited the ligands‘ wideband emission.     

Synthesis and characterization of Eu3+ doped Gd2O3 nanotubes using multi wall carbon nanotubes as removable templates

Eu³⁺ doped Gd₂O₃ nanotubes have been synthesized using multi wall carbon nanotubes as removable templates by employing a liquid phase deposition method. The prepared Eu³⁺ doped Gd₂O₃ nanotubes were characterized by means of x-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy, fourier transform infrared sepctroscopy and thermogravimetry and differential thermal analysis. XRD patterns conrm the cubic phase of Eu³⁺ doped Gd₂O₃ nanotubes. From the measured SEM images, the average diameter of the Eu³⁺: Gd₂O₃ nanotubes were estimated to be in the range of 50–70 nm. The photoluminescence analysis revealed that the Eu³⁺: Gd₂O₃ nanotubes can display a strong red emission peak at around 616 nm, due to the ⁵D₀→⁷F₂ electric dipole transition of Eu³⁺ ions. Such luminescent powders are expected to find potential applications in fluorescent lamps and display device applications.     

Luminescence properties of Eu and Eu doped calcium-deficient hydroxyapatite prepared in air

Eu-doped calcium-deficient hydroxyapatite Ca_8.95Eu_0.05HPO₄(PO₄)₅OH (designated CDHA:Eu) was prepared via the coprecipitation method and calcined in air. Phase purity, crystal structure and morphology of the CDHA:Eu were characterized using X-ray diffraction spectrometer and scanning electron microscopy. The photoluminescence excitation and emission spectra of Eu²⁺ and Eu³⁺ ions were measured using luminescence spectrometer. The emission spectra showed a broad emission band centered at 450 nm corresponded to the typical 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ions, and sharp peaks corresponded to the ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, 4) transitions of Eu³⁺ ions. This research was focused on the site-distribution of Eu³⁺ ions. The Eu³⁺ in different sites had different spectroscopic features and the charge compensation mechanisms were also discussed.