2,4,6-三吡啶基三嗪-铽、钐配合物的合成、表征及荧光性能研究(英文)

分别以对羟基苯甲酸、对苯二甲酸和2,4,6-三吡啶基三嗪为配体,铽、钐为中心合成了两个系列共10种配合物。对所合成的配合物进行了元素分析、电导率测定、紫外光谱和红外光谱的测试,推测其组成分别为:RE(TPTZ)(NO3)3(C2H5OH)·H2O,RE(TPTZ)2(NO3)3(C2H5OH)·H2O,RE2(TPTZ)(NO3)6(C2H5OH)·2H2O,RE(TPTZ)(C7H5O3)3(C2H5OH)·2H2O和RE2(TPTZ)2(C8H4O4)(NO3)4(C2H5OH)·H2O(RE=Tb,Sm)。硝酸根、芳香酸的氧原子以及TPTZ的主配位点氮原子与稀土离子成键。对羟基苯甲酸的三重态能级及配合物的荧光测试表明,虽然对羟基苯甲酸三重态能级低于Tb3+和Sm3+离子的最低激发态能级,但该配体和具有芳香环的配体TPTZ耦合,能与Tb3+和Sm3+离子形成发光较好的稀土配合物。对苯二甲酸对铽和钐配合物的荧光增强最大,同时,稀土离子浓度高则荧光强度也高,在这两个系列配合物中未见浓度猝灭现象。     

水热法制备形貌可控的ZnMoO4微晶及其光致发光性能

以Zn(Ac)2和(NH4)6Mo7O24.4H2O为原料,分别以CTAB、SDS、PVP-K30作为辅助剂,采用水热法合成了不同形貌和结构的ZnMoO4微晶。使用X射线衍射(XRD)、扫描电镜(SEM)及光致发光光谱(PL)等分析手段对所得材料的结构、形貌及发光性能进行了分析和表征。测试结果表明:通过改变辅助剂的种类、用量和反应时间可以合成形貌可控的ZnMoO4微晶,不同形貌的样品发光强度不同,但发射中心均在565 nm左右。     

耐高温型4-卤代(氟、氯)苯甲酸铽配合物的合成及荧光性能研究

以4-氟苯甲酸(4-FBA)、4-氯苯甲酸(4-ClBA)为配体制备了具有良好热稳定性的稀土配合物Tb(4-FBA)3·2H2O和Tb(4-ClBA)3·2H2O,与前期工作中合成的Tb(4-BrBA)3的紫外及荧光光谱进行了分析比较。紫外-可见光吸收光谱表明,相同浓度下,3种配合物的紫外吸收能力以Tb(4-FBA)3·2H2O、Tb(4-ClBA)3·2H2O、Tb(4-BrBA)3顺序依次增大。液体荧光光谱表明,Tb(4-ClBA)3·2H2O的荧光发射强度最强。从配体的能级、配合物的紫外吸收能力及能量传递过程中的热振动损耗等方面对实验结果进行了讨论分析。热重分析表明,Tb(4-FBA)3·2H2O和Tb(4-ClBA)3·2H2O在450℃出现快速分解。将2种配合物放置于马弗炉中350℃加热1 h后,发现Tb(4-FBA)3·2H2O的荧光发射强度降低了24%,Tb(4-ClBA)3·2H2O荧光发射强度仅降低了13%左右,表明2种配合物高温条件下分子结构保持稳定,加热后2种配合物的红外光谱也表明2种配合物在高温条件下未发生分解。     

单分子磁体

单分子磁体指的是那些在阻塞温度以下出现磁化强度慢弛豫的分子。自从1993 年报道了 第一例单分子磁体[Mn12O12(O2CCH3)16(H2O)4] ￠ 4H2O ￠ 2CH3CO2H (Mn12) 以来,人们在探索 新颖的单分子磁体及其在信息存储、自旋电子学和量子计算等方面的潜在应用方面付出了极大的努 力,已经合成得到许多具有单分子磁体性质的单核和多核金属簇合物。本文将重点介绍基于氧桥联 的锰或铁簇合物、单核过渡金属化合物以及稀土配合物的单分子磁体。     

Ce（Ⅲ）,Dy（Ⅲ）与四异丙基亚甲基双膦酸酯配合物的合成与光谱表征

在乙腈溶液中合成了三种镧系金属三氟甲基磺酸盐Ln(OTf)3(Ln=Ce,Dy)与四异丙基亚甲基双膦酸酯[L=(iPrO)2P(O)CH2P(O)(iPrO)2]配合物[CeL4](OTf)3.2H2O,[Dy(OTf)2L2(H2O)2](OTf)(CH3CN)和[DyL4](OTf)3.L.2H2O。荧光分析发现,[CeL4](OTf)3.2H2O在波长249和300 nm激发下,测得641 nm处有明显的发射峰,Dy3 的两种配合物中[Dy(OTf)2L2(H2O)2](OTf)(CH3CN)中有水参与配位,使得其发射和激发峰的强度均弱于没有水参与配位的[DyL4](OTf)3.L.2H2O。另外,通过元素分析,热重分析,红外光谱和核磁共振等手段对配合物进行了组成确定和光谱学表征,并初步确定了膦氧配体与稀土离子的配位模式。这三种配合物均是八配位模式,[CeL4](OTf)3.2H2O和[DyL4](OTf)3.L.2H2O呈现高的对称性,4个L配体作为双齿配体全部参与配位,而[Dy(OTf)2L2(H2O)2](OTf)(CH3CN)中Dy3 周围除两个L和两个OTf外,还有2个配位水。     

一种新颖的稀土-2-羟基烟酸的配合物的结构和光谱性质研究

通过水热反应合成了一种新颖的稀土2-羟基烟酸的配合物{[LaL(HL)(H2O)3]1/3(SO4)2/3(H3O)2H2O}(H2L=2-hydroxynicotinic acid)。X-ray单晶衍射分析可知,2-羟基烟酸通过羧基O和羟基O原子桥连La离子,形成二维层状结构,层与层之间通过弱作用力拓展为三维结构。二维相关光谱分析表明N—H面外弯曲振动和C—H面外弯曲振动对磁微扰比较敏感,这可能是吡啶环上π电子云在磁微扰下变形引起C—H和N—H面外弯曲振动的响应,SO24-的ν4振动和羧基不对称伸缩振动对磁微扰也比较敏感;热微扰下N—H伸缩振动比较敏感。此外还对化合物进行了紫外和热重分析。     

羧酸类钕(Ⅲ)配合物的合成、热稳定性和荧光性能研究

为了开发稀土有机配合物作为激光工作物质,分别以均苯三甲酸(H3BTC)、苯六甲酸(H6MTA)和1,2,3,4,5,6-环己六甲酸(H6CCA)为配体合成了三种Nd(Ⅲ)的二元发光配合物。通过元素分析、等离子体原子发射光谱和红外光谱对其化学组成进行了结构表征,确定其化学结构依次为Nd(BTC)·4H2O,Nd2(MTA)·6H2O和Nd2(CCA)·4H2O,并对其热稳定性和荧光性能进行了分析测试。三种配合物的发射谱均有三个带状谱带,位于近红外区,其对应于Nd(Ⅲ)离子的特征跃迁4F3/2→4I9/2,4F3/2→4I11/2和4F3/2→4I13/2。结果表明,羧酸类钕(Ⅲ)配合物在近红外区具有明显的特征发射,具有良好的热稳定性和较好的发光性能,可以作为潜在的激光介质。     

稀土、2,2''''-联吡啶、邻氨基苯基苯甲酸配合物合成、光谱表征及荧光性质

2,2'-联吡啶(bipy)、邻氨基苯基苯甲酸(HL)与稀土离子(RE=Tb,Eu,Sm,Nd)合成了固体稀土配合物.用元素分析、摩尔电导、紫外光谱、红外光谱、差热-热重分析和荧光光谱,对配合物的组成进行了确定和表征,并对TbL3和TbL3·bipy·3H2O的荧光性能进行了测试和讨论.TbL3·bipy·3H2O的荧光强度比TbL3的荧光强度强.     

均苯三甲酸铕掺杂配合物的合成及其荧光性能

合成了两个系列的均苯三甲酸铕配合物。其一是以均苯三甲酸(H3btc)为配体,Eu3+及掺杂过渡金属Zn2+、Cd2+、Mn2+、N i2+为中心离子的配合物;其二是以均苯三甲酸、邻菲啰啉(Phen)为配体,Eu3+及掺杂Y3+、La3+、Gd3+为中心离子的异核稀土配合物。对配合物进行了元素分析、差热-热重、红外光谱、紫外光谱、荧光寿命及荧光性能等方面的测试分析。配合物的组成分别为:EuL.6H2O(1)、EuLL1.′5.2H2O(2)、Eu0.5Y0.5LL1.′5.3H2O(3)、Eu0.5La0.5LL1.′5.3H2O(4)、Eu0.5Gd0.5LL1.′5.3H2O(5)、EuZnLC l2(C2H5OH)2.2H2O(6)、EuCdLC l2-(C2H5OH)2.5.2H2O(7)、EuMnLC l2(C2H5OH)2.2H2O(8)、EuN iLC l2(C2H5OH)2.2H2O(9)(其中L=btc,L′=Phen)。均苯三甲酸的羧酸氧原子和邻菲啰啉的氮原子与稀土离子配位。差热-热重的测试结果表明,均苯三甲酸-邻菲啰啉异核稀土配合物的分解温度为490℃,铕掺杂过渡金属配合物分解温度为450℃,两类配合物的最终分解产物均为氧化物。荧光光谱的测试结果表明,三元配合物EuLL1.′5.2H2O(2)的荧光强度明显高于二元配合物EuL.2H2O(1);配合物(3)、(4)、(6)、(7)中,Y3+、La3+、Zn2+、Cd2+无未充满的d层或f层电子,对Eu3+的荧光有增强作用;配合物(5)中的Gd3+有4 f7半充满稳定电子层结构,对Eu3+的荧光也有增强作用。在配合物(8)和(9)中,Mn2+和N i2+的未充满d层电子消耗配体吸收的能量,对Eu3+的荧光有猝灭作用。     

稀土、2,2’-联吡啶、邻氨基苯基苯甲酸配合物合成、光谱表征及荧光性质

2,2’-联吡啶(bipy)、邻氨基苯基苯甲酸(HL)与稀土离子(RE=Tb,Eu,Sm,Nd)合成了固体稀土配合物。用元素分析、摩尔电导、紫外光谱、红外光谱、差热-热重分析和荧光光谱,对配合物的组成进行了确定和表征,并对TbL3和TbL3·bipy·3H2O的荧光性能进行了测试和讨论。TbL3·bipy·3H2O的荧光强度比TbL3的荧光强度强。     

Computer modelling of defects and dopants in mixed metal fluorides

This paper describes a computer modelling study of rare earth doping in the mixed metal fluorides LiCaAlF 6 , LiSrAlF 6 and LiYF 4 . All these materials have potential technological applications, providing the motivation to improve understanding of their defect chemistry; in particular the energetics of doping and the sites occupied by dopant ions. Computer modelling is used to calculate the effect of rare earth dopant concentration on the structure of LiYF 4 , and to predict the sites occupied by rare earth dopants and the corresponding form of charge compensation, in LiCaAlF 6 and LiSrAlF 6 .     

Electrical relaxation in rare earth doped cubic lead fluoride

Audio frequency complex impedance measurements are performed over the temperature range 5.5-380 K on lead fluoride doped with ten rare earths and lanthanum at various concentrations. It is found that the complexity of the relaxation spectrum increases as the size of the trivalent ion decreases. Specifically, for the largest rare earths, only one relaxation is found. That relaxation is different from the cases in the alkaline earth fluorides where only one relaxation is observed in that the reorientation enthalpy depends strongly upon ion size. Double-doped samples are studied to determine whether the relaxation is due to a simple site or a cluster. For the smallest rare earths, however, at least nine relaxations are found. The concentration studies indicate multiple relaxations for certain sites. Both simple sites and clusters are observed for small rare earths.     

Relaxation modes of point defect pairs in ionic crystals: Approximate solutions for the threeshell model

A perturbation technique is used to obtain first-order expressions for the relaxation frequencies for the relaxation modes of the three-shell model of pairs of coupled defects moving on the same fcc lattice (e.g. divalent cation-cation vacancy in the rocksalt structure) or on interpenetrating fcc lattices (vacancy pairs in the rocksalt structure, or interstitial anion—excess valency cation in the fluorite structure). For the dielectrically-active T_lu modes, expressions are given for the relaxation intensities in the zero-order approximation. These results are then used to discuss experimental data for NaCl and KCl containing divalent cations and for alkaline earth fluorides containing trivalent rare earth ions.     

NMR parameters in column 13 metal fluoride compounds (AlF3, GaF3, InF3 and TlF) from first principle calculations

The relationship between the experimental ¹⁹F isotropic chemical shift and the ¹⁹F isotropic shielding calculated using the gauge including projector augmented-wave (GIPAW) method with PBE functional is investigated in the case of GaF₃, InF₃, TlF and several AlF₃ polymorphs. It is shown that the linear correlation between experimental and DFT-PBE calculated values previously established on alkali, alkaline earth and rare earth of column 3 basic fluorides (Sadoc et al., Phys. Chem. Chem. Phys. 13 (2011) 18539–18550) remains valid in the case of column 13 metal fluorides, indicating that it allows predicting ¹⁹F solid state NMR spectra of a broad range of crystalline fluorides with a relatively good accuracy. For the isostructural α-AlF₃, GaF₃ and InF₃ phases, PBE-DFT geometry optimization leads to noticeably overbended M–F–M bond angles and underestimated ²⁷Al, ⁷¹Ga and ¹¹⁵In calculated quadrupolar coupling constants. For the studied compounds, whose structures are built of corner shared MF₆ octahedra, it is shown that the electric field gradient (EFG) tensor at the cationic sites is not related to distortions of the octahedral units, in contrast to what previously observed for isolated AlF₆ octahedra in fluoroaluminates.     

提高土铕配合物发光性质研究简

将稀土铕配合物Eu（BA）3（TPPO）2分别组装到未修饰和修饰的介孔分子筛（SBA-15）中,详细地表征了样品的形貌和结构,系统地研究了其光致发光性质和稳定性,并与纯的稀土配合物进行比较研究。研究结果表明,SBA-15为组装的稀土配合物提供了良好的刚性环境,组装后的稀土铕离子配合物的光致发光稳定性比纯的配合物的光致发光稳定性有很大的提高。这将使稀土配合物在分子光学、电子器件等诸多领域具有重要的应用前景。     

Equation of state and temperature variation of the bulk modulus of the alkaline earth fluorides

The isotherms for the alkaline earth fluorides (CaF₂, SrF₂ and BaF₂) have been computed using the expression for the total free energy of a crystal in the quasiharmonic approximation. The theoretical points for SrF₂ and BaF₂ have been compared with the points derived from Bridgman’s experimental relation. The temperature variation of the isothermal bulk modulus of the alkaline earth fluorides has been worked out on the basis of Axe’s shell model. The theoretica points are compared with the points obtained from the temperature variation of the elastic constants data. It is found that the vibrational contribution to the temperature variation of the elastic constants in these crystals is significant.     

发射光谱测定微量稀土杂质用的一种新的载体KBH4的研究

介绍了高纯稀土氧化物中微量稀土杂质的光谱测定方法，本工作用碳粉做缓冲剂，ＫＢＨ４做载体，用化学方法将大量稀土分离掉，而后对余下微量和稀土杂质进行光谱测定。只要取样量不少于１克，则可测定的纯度为９９．９９９９５％的稀土样品。     

Anisotropy of the ionic conductivity and dielectric response in orthorhombic and monoclinic inorganic fluorides

The anisotropy of the ionic conductivity and permittivity of (1) BaR₂F₈ (R=rare earth element) single crystals with monoclinic BaTm₂F₈ structure and of (2) (β-YF₃ structured) rare earth trifluorides is studied. Single crystals, eutectic composites and ceramics are investigated in a broad temperature range. In the monoclinic BaR₂F₈ crystals, a pronounced anisotropy of the ionic conductivity and a slight anisotropy of the permittivity are found. The fastest ionic transport with the lowest activation energy (0.563 eV) and the highest value of the permittivity are observed along thea axis. The temperature dependencies of the fluoride ion conductivities of various orthorhombic rare earth trifluorides differ only slightly from one another. For the bulky single crystals, the conductivity at 500 °C and the conduction activation enthalpy are equal to 1.1(4)×10⁻⁵ S/cm and 0.75(3) eV, respectively. The ionic conductivity is almost isotropic, but the anisotropy of the permittivity is significant. For the fluorides of both structural types, plausible conduction mechanisms are proposed, networks of most probable conduction paths are presented and the origin of the observed anisotropy of the ionic conductivity is elucidated. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997     

On the structural phase transition in rare earth elpasolites

The structural phase transition in two representatives of the rare earth elpasolite fluorides, Rb₂NaHoF₆ and Rb₂NaTmF₆, are studied in detail. The symmetry of the soft mode is determined from Raman spectra, X-ray and neutron powder diffraction data to be ₄ ⁺ . From the temperature dependence of the elastic constants of both compounds, estimates of various phase transition parameters are given, e.g. strain soft mode coupling constant and soft mode frequency. The softening of the elastic constants forT>T _c is explained by the strain coupling to the fluctuations of the soft mode coordinates. The energy of the soft phonon at the zone boundary is estimated from the data and compared with that of K₂ReCl₆. The phase transition mechanisms in rare earth elpasolites and hexahalometallates are discussed.     

稀土对镁合金应力腐蚀影响电子理论研究

建立了镁合金纯净晶界及其析出Mg₁₇Al₁₂相的晶界原子集团，应用实空间的递归方法计算了铝、稀土元素在晶界的偏聚能，晶界处铝、稀土原子间相互作用能和不同体系的费米能级.讨论了铝、稀土在晶界的偏聚行为，铝、稀土原子间的相互作用与有序化的关系及稀土对镁合金晶间应力腐蚀影响的物理本质.研究发现：铝、稀土原子偏聚于晶界；铝原子间相互排斥，在晶界区形成有序相Mg₁₇Al₁₂，稀土原子间互相吸引，形成原子团簇；稀土原子团吸引铝原子，使铝原子渗入稀土团簇中，形成稀土化合物.因此，稀土具有抑制铝在晶界形成导致应力腐蚀的阴极相Mg₁₇Al₁₂的作用，提高镁合金的晶间应力腐蚀抗力. 关键词： 电子理论 镁合金 应力腐蚀 稀土