Slow Relaxation of the Magnetization in Anilato-Based Dy(III) 2D Lattices

The search for two- and three-dimensional materials with slow relaxation of the magnetization (single-ion magnets, SIM and single-molecule magnets, SMM) has become a very active area in recent years. Here we show how it is possible to prepare two-dimensional SIMs by combining Dy(III) with two different anilato-type ligands (dianions of the 3,6-disubstituted-2,5-dihydroxy-1,4-benzoquinone: C₆O₄X₂²⁻, with X = H and Cl) in dimethyl sulfoxide (dmso). The two compounds prepared, formulated as: [Dy₂(C₆O₄H₂)₃(dmso)₂(H₂O)₂]·2dmso·18H₂O (1) and [Dy₂(C₆O₄Cl₂)₃(dmso)₄]·2dmso·2H₂O (2) show distorted hexagonal honeycomb layers with the solvent molecules (dmso and H₂O) located in the interlayer space and in the hexagonal channels that run perpendicular to the layers. The magnetic measurements of compounds 1, 2 and [Dy₂(C₆O₄(CN)Cl)₃(dmso)₆] (3), a recently reported related compound, show that the three compounds present slow relaxation of the magnetization. In compound 1 the SIM behaviour does not need the application of a DC field whereas 2 and 3 are field-induced SIM (FI-SIM) since they show slow relaxation of the magnetization when a DC field is applied. We discuss the differences observed in the crystal structures and magnetic properties based on the X group of the anilato ligands (H, Cl and Cl/CN) in 1–3 and in the recently reported derivative [Dy₂(C₆O₄Br₂)₃(dmso)₄]·2dmso·2H₂O (4) with X = Br, that is also a FI-SIM.     

具有双螺旋链结构的3-吡啶丙烯酸镝配合物的水热合成及晶体结构

采用水热法制备了一种新型稀土配位聚合物[Dy(3-PA)3(H2O)]n(3-PA=3-吡啶丙烯酸)(1),并通过X射线单晶衍射结构分析、元素分析、红外光谱、热重分析对配合物1进行了结构表征.结构分析表明,标题配合物属于三斜晶系,Pī空间群,晶胞参数为:a=0.617 16(5)nm,b=1.270 45(11)nm,c=1.564 03(13)nm,α=111.557 0(10)°,β=90.307 0(10)°,γ=95.342 0(10)°,V=1.134 54(16)nm3,Z=2.金属离子Dy(III)通过配体3-AP羧基的桥联作用,链接成为一维双螺旋链状配位聚合物.     

Ba_3(PO_4)_2:Ce~(3+),Dy~(3+)荧光粉的组成与发光特性研究

在活性炭还原气氛下高温固相法合成了Ba3(PO4)2:Ce3+,Dy3+紫外发射荧光粉。XRD图谱表明,烧结温度为1100℃时保温处理3 h,样品为单相的Ba3(PO4)2型六方晶系结构。荧光光谱显示:单掺Ce3+样品中,Ce3+掺杂浓度为8%(摩尔分数)时样品的发光最强,发射峰的位置处在350 nm附近(Ce3+的2D→2F5/2和2D→2F7/2跃迁发射)。适量的Sr2+取代部分Ba2+离子,改变了基质晶格环境,使样品的发光强度得到提高且发射峰向长波方向红移。引入Dy3+作为敏化剂,样品发射峰红移到386 nm,亮度增强,主要是由于Dy3+和Ce3+之间发生了有效的能量传递过程。确定了Dy3+的最佳掺杂浓度为3%,发光强度提高了27%。     

Study of TL properties of LaAlO3:Ce,Dy crystals for UV dosimetry

Thermoluminescence properties of lanthanum aluminum oxide (LaAlO₃) crystals doped with optically active rare earth ions have been investigated for ultraviolet dosimetry purposes. Single crystals co-doped with 5.0 at.% of Ce³⁺ and 1.0 at.% of Dy³⁺ ions have two thermoluminescent (TL) peaks at 151 °C and 213 °C which can be sensitized after 1 h of UV exposure. The material shows very high TL output and linear response for UV spectral irradiance ranging from 0.04 to 1.20 mJ cm⁻², that corresponds to 10 times the TL response of the Al₂O₃:C oxides. From 0.62 to 148.0 mJ cm⁻² the dependence is linear with the logarithm of the spectral irradiance. The investigation demonstrates that LaAlO₃:Ce,Dy crystals are very attractive to be investigated as UV dosimeters.     

Comparative evaluation of Dy(III) selective poly(vinyl) chloride based membrane electrodes of macrocyclic tetraimine Schiff's bases

Three different derivatives of macrocyclic tetraimine Schiff's base have been synthesized and explored as a neutral ionophores for preparing poly(vinyl chloride) based membrane sensors selective to Dy³⁺. The addition of sodium tetraphenyl borate and various plasticizers, viz., o-NPOE, DBP, DBBP, DOP and CN has been found to substantially improve the performance of the sensors. The best performance was obtained with the sensor no. 1 having membrane of Schiff's base (SL-1) with composition (w/w) SL-1 (4.5%): PVC (30.5%): o-NPOE (59.5%): NaTPB (5.5%). This sensor exhibits Nernstian response with slope 19.4 mV/decade of activity in the concentration range of  10⁻⁸ to 1.0 × 10⁻² M Dy³⁺, performs satisfactorily over wide pH range of (2.8-7.2) with a fast response time (10 s). The sensor was also found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of acetonitrile, methanol or ethanol. The proposed sensor can be used over a period of 1.5 months without significant drift in potentials. The sensor has been also utilized for the determination of Dy³⁺ level in different soil samples.     

Resolving the black-hole information paradox by treating time on an equal footing with space

Pure states in quantum field theory can be represented by many-fingered block-time wave functions, which treat time on an equal footing with space and make the notions of “time evolution” and “state at a given time” fundamentally irrelevant. Instead of information destruction resulting from an attempt to use a “state at a given time” to describe semi-classical black-hole evaporation, the full many-fingered block-time wave function of the universe conserves information by describing the correlations of outgoing Hawking particles in the future with ingoing Hawking particles in the past.     

Interrelation of intrinsic and extrinsic defects – congruent, stoichiometric, and regularly ordered lithium niobate

A new approach to the intrinsic and extrinsic defect subsystems, considering them as one integrated functional system, is developed for complex oxides. The strong interrelation of these subsystems becomes especially apparent when concentrations of both defect classes are comparable. A new parameter, reflecting the total intrinsic defect concentration, is introduced to determine the degree of crystal imperfection. The necessity of at least two calibrated samples – congruent and regularly ordered crystals – is substantiated. The accuracy by which the parameter can be determined can serve as a criterion in comparison of different methods of crystal characterisation. A procedure for crystal calibration by several physical characteristics is illustrated. Such a heuristic generalisation of the concept of mutual correlation of the whole defect system and the material only became possible on the basis of experimental and theoretical study of large numbers of LiNbO₃ crystals. The spectra of EPR, NMR, ENDOR, and other properties of crystals with different compositions, diverse modifiers (K, Mg,...), and various probe impurities have been analysed. It is found that crystals with vanishingly small concentration of intrinsic defects offer extraordinary informative opportunities. Their micro- and macroscopic properties are discussed. The developed ideas have a general character; therefore they should also be valid for other non-stoichiometric complex oxides. Received: 3 December 1998 / Revised version: 15 February 1999 / Published online: 12 April 1999     

Proton-exchange influence on the polar phonons of LiTaO3 optical waveguides

Refractive index change and Raman scattering of Z-cut proton-exchanged LiTaO₃ optical waveguides with different composition have been studied. Probing of the waveguide depth was carried out by using micro-Raman spectroscopy in order to distinguish layers with different phase states. Varying the proton-exchange and post-exchange annealing regimes, two phases –α and β– in addition to the pure LiTaO₃, were clearly observed. The behaviour of the A ₁ vibrations of the TaO₆ groups was found to be very sensitive to the phase changes. Using data from waveguide Raman spectra, normal and oblique E(TO, LO) phonons were sorted and their properties were followed in the α and β phases. The OH-stretchings are considered to correspond to dipoles turned out of the oxygen planes. Received: 9 July 1999 / Accepted: 11 October 1999 / Published online: 24 March 2000     

Dy3+含量对Eu2+,Dy3+共掺高硅氧发光玻璃发光性能的影响

通过控制Dy3+的掺杂浓度,制备出了不同浓度的Eu2+,Dy3+单掺和共掺高硅氧发光玻璃,测试其激发和发射光谱,讨论了Dy3+浓度对Eu2+,Dy3+共掺样品发光性质的影响。结果表明,Eu2+,Dy3+共掺高硅氧发光玻璃中存在Dy3+向Eu2+的无辐射能量传递现象,且Dy3+的引入会使高硅氧发光玻璃中Eu—O的共价作用减弱,造成Eu2+发射峰蓝移;随着Dy3+浓度的增加,Dy3+→Eu2+能量传递增强,Eu2+发光增强;Dy3+含量继续增加,则Dy3+发光出现浓度猝灭,且Dy3+→Eu2+能量传递减弱。     

Ultraviolet and blue NaHg and NaCd excimer bands

We present the current-reversal spectra of the high pressure Na-Hg-Xe and Na-Cd-Xe lamps, from which the specific NaHg and NaCd structured continua have been observed. Detailed analysis revealed the existence of additional structure in the case of NaCd and NaHg blue diffuse bands. In the NaHg case the neighbourhood of the 330 nm sodium line revealed two satellite bands of NaHg origin, but almost no structure around the 330 nm sodium atomic line was found in the case of Na-Cd-Xe discharge lamp.