香豆素β-二酮、邻菲罗啉、铕三元配合物的合成及发光性能研究

通过3-乙酸乙酯香豆素与3-乙酰基香豆素的克莱森缩合反应。合成了香豆素β-二酮化合物,并与邻菲罗啉、铕（Ⅲ）反应合成了一种新型三元铕配合物,利用红外光谱、紫外光谱、元素分析对三元铕配合物的组成和结构进行了表征,用荧光光谱检测其荧光发光性能。     

1,1,1-三[(2''''-甲酰苄胺苯氧)甲基]对甲苯磺酰氨基甲烷的合成及其稀土配合物的荧光性质

合成了一个新的三足芳香酰胺型有机配体1，1，1-三[（2’-甲酰苄胺苯氧）甲基]对甲苯磺酰氨基甲烷，及其Eu（NO3）3和Tb（NO3）3的配合物，并通过元素分析、红外光谱、核磁共振氢谱和摩尔电导率进行了表征。室温下还研究了配合物的固体荧光性质，结果表明，两个配合物均能表现其稀土离子的特征荧光，但铽配合物的荧光要明显强于铕配合物，说明配体与铽之问的能级匹配要比铕好。     

1,1,1-三[(2′-甲酰苄胺苯氧)甲基]对甲苯磺酰氨基甲烷的合成及其稀土配合物的荧光性质

合成了一个新的三足芳香酰胺型有机配体1,1,1-三[(2′-甲酰苄胺苯氧)甲基]对甲苯磺酰氨基甲烷,及其Eu(NO3)3和Tb(NO3)3的配合物,并通过元素分析、红外光谱、核磁共振氢谱和摩尔电导率进行了表征。室温下还研究了配合物的固体荧光性质,结果表明,两个配合物均能表现其稀土离子的特征荧光,但铽配合物的荧光要明显强于铕配合物,说明配体与铽之间的能级匹配要比铕好。     

铕（III）-1-（氯苯基）-3-（2-羟基苯基）-丙二酮类配合物的合成与荧光性质

合成了1-(邻氯苯基)-3-(2-羟基苯基)-丙二酮(L1)、1-(间氯苯基)-3-(2-羟基苯基)-丙二酮(L2)和1-(对氯苯基)-3-(2-羟基苯基)-丙二酮(L3)3种配体,并将此3种配体分别与 Eu(III)反应生成3种新的稀土配合物。运用元素分析、红外光谱与荧光光谱等手段对配合物进行了表征。结果表明：3种配合物的组成分别为 Eu(L1)3·2H2O、Eu(L2)3·2H2O 和 Eu(L3)3·2H2O。荧光光谱显示,3种配合物的配体均能将吸收的能量有效地传递给三价铕离子,从而使配合物发射出强的铕离子的特征荧光。在3种配合物中,Eu(L1)3·2H2O 的荧光强度远大于 Eu(L2)3·2H2O 和 Eu(L3)3·2H2O 的荧光强度,这说明配体 L1与 Eu(III)离子的能级匹配较好,能量传递效率较高。     

铕(Ⅲ)-1-(氯苯基)-3-(2-羟基苯基)-丙二酮类配合物的合成与荧光性质

合成了1-(邻氯苯基)-3-(2-羟基苯基)-丙二酮(L1)、1-(间氯苯基)-3-(2-羟基苯基)-丙二酮(L2)和1-(对氯苯基)-3-(2-羟基苯基)-丙二酮(L3)3种配体,并将此3种配体分别与Eu(III)反应生成3种新的稀土配合物。运用元素分析、红外光谱与荧光光谱等手段对配合物进行了表征。结果表明:3种配合物的组成分别为Eu(L1)3·2H2O、Eu(L2)3·2H2O和Eu(L3)3·2H2O。荧光光谱显示,3种配合物的配体均能将吸收的能量有效地传递给三价铕离子,从而使配合物发射出强的铕离子的特征荧光。在3种配合物中,Eu(L1)3·2H2O的荧光强度远大于Eu(L2)3·2H2O和Eu(L3)3·2H2O的荧光强度,这说明配体L1与Eu(III)离子的能级匹配较好,能量传递效率较高。     

8-羟基喹哪啶-丙烯酸-铕(Ⅲ)的合成及其光致发光性质研究

用载流子传输性能较好的8-羟基喹哪啶和可聚合的丙烯酸为配体,合成了8-羟基喹哪啶-丙烯酸-铕(Ⅲ),并用TFIR、EA和^1HNMR进行了表征。所合成的配合物能发出较强的Eu^3 的特征荧光,说明8-羟基喹哪啶和丙烯酸对铕离子具有敏化作用。此单体具有聚合活性。     

3-氨基吡嗪-2-羧酸镍配合物的合成与结构

以3-氨基吡嗪-2-羧酸(3-Hapzac)为配体合成了一个镍的配合物[Ni(3-apzac)_2(H_2O)_2],并利用元素分析、IR以及X射线单晶衍射等手段对配合物进行了表征。在配合物中,配位的水分子、羧基和与氨基都参与形成了氢键,通过强的氢键相互作用使配合物形成了三维超分子网络结构。     

三嗪含硫羧酸金属配合物的合成及性质表征

以三聚硫氰酸为母体,与氯乙酸反应得到了具有三个羧基的柔性羧酸配体2,2',2″-[1,3,5-三嗪-2,4,6-三(硫代)]三乙酸(H_3TTTA),利用该配体分别与过渡金属盐反应得到了六种配合物,对配体和配合物分别进行~1H-NMR、元素分析、IR、TG的表征,推测了配合物的结构。这为后期三嗪含硫羧酸金属配合物在功能材料、生命科学等领域的应用研究提供理论基础。     

新型稀土Eu3+四元配合物的制备及荧光性能研究

以稀土Eu~(3+)为中心离子,2,6-二(4-乙氧基苯甲酰基)吡啶(L)、1,10-邻菲罗啉(Phen)、丙烯腈(AN)和三苯基氧膦(TPPO)为配体,制备了EuL(Phen)_2、EuL(Phen)_2TPPO和EuL(Phen)_2AN三种配合物,其中EuL(Phen)_2AN为新型四元配合物。结构通过红外光谱进行表征。通过荧光光谱仪分析三种配合物的荧光性能,结果表明,新型四元配合物EuL(Phen)_2AN在594,617 nm处出现Eu~(3+)特征发射峰,617 nm处峰值最大,两处峰值的比值为2.18,说明配合物单色性好,是一种合适的红光材料;荧光强度大小顺序为EuL(Phen)_2EuL(Phen)_2ANEuL(Phen)_2TPPO;EuL(Phen)_2AN在不同溶剂中的荧光强度呈现一定规律性,即溶剂的偶极矩极性与体系的荧光强度值成反比。     

1-苯基-3-二茂铁基β-二酮、铕、丙烯酸稀土三元配合物的荧光猝灭原因研究

文章通过计算机分子模拟的方法对1-苯基-3-二茂铁基β-二酮、铕、丙烯酸稀土三元配合物荧光猝灭的原因进行研究。结果发现配体中引入二茂铁基后,配体的最低激发三重态能级低于稀土离子的激发态能级,不能够满足稀土配合物发光的必要条件,证明配体中二茂铁基的引入是导致稀土配合物荧光猝灭的原因。     

Ferroelectric Ceramics in the PbMg1/3Nb2/3O3-PbCd1/3Nb2/3O3 System

Solid solutions (1-x)PbMg_1/3Nb_2/3O₃ + xPbCd_1/3Nb_2/3O₃ with x = 0-0.30 are investigated with purpose to work out a capacitor ceramics with good dielectric properties and low sintering temperature. It is found that the perovskite phase forms at sintering near to 980°C and begins to decompose at higher temperatures. When x grows from 0 to 0.30, the Curie temperature linearly grows from -10°C to +25°C, the dielectric permittivity ε_m in the Curie point T_C decreases from 18000 to 6800 and the phase transition becomes more diffused. The dielectric permittivity at room temperature is rather high and the temperature stability is improved. The system is of interest, because it can serve as a base for working out some ceramic materials for capacitors with low sintering temperature, which needs of no special atmosphere at burning.     

3-叠氮甲基-3-甲基氧丁环的合成

以三羟甲基乙烷与碳酸二乙酯为原料,经环化反应合成了3-羟甲基-3-甲基氧丁环(HMM O)。在低温下,HMM O与对甲苯磺酰氯反应生成3-磺酸酯甲基-3-甲基氧丁环(M TM O)。M TM O和叠氮化钠发生叠氮化反应形成叠氮单体3-叠氮甲基-3-甲基氧丁环(AMM O)。三步反应收率分别为76%,96%,85%。用核磁、红外、元素分析和DSC表征了化合物的结构与性能。结构鉴定表明为目标化合物AMM O。     

3-溴甲基-3-甲基氧杂环丁烷的合成

以2,2-二溴甲基丙醇（BBMP）为初始原料,通过与碱发生关环反应生成3-溴甲基-3-甲基氧杂环丁烷（BrMMO）。讨论了碱的种类和用量对BBMP关环产率的影响以及反应体系中碱的浓度、反应温度和反应时间对合成BrMMO产率的影响。通过实验确定的最佳工艺条件为：BBMP与NaOH摩尔比为1.0∶1.1,NaOH醇溶液的质量分数为12%,反应温度为78℃,反应时间为4h时,BrMMO产率为65%。最终产品经元素分析、IR和1HNMR检测确定为BrMMO。该试验工艺简单,原料易得,且溶剂便于回收、污染小。     

Tunable color emission in LaScO3:Bi3+,Tb3+,Eu3+ phosphor

LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ (x = 0 − 0.04, y = 0 − 0.05, z = 0 − 0.05) phosphors were prepared via high-temperature solid-state reaction. Phase identification and crystal structures of the LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ phosphors were investigated by X-ray diffraction (XRD). Crystal structure of phosphors was analyzed by Rietveld refinement and transmission electron microscopy (TEM). The luminescent performance of these trichromatic phosphors is investigated by diffuse reflection spectra and photoluminescence. The phenomenon of energy transfer from Bi³⁺ and Tb³⁺ to Eu³⁺ in LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ phosphors was investigated. By changing the ratio of x, y, and z, trichromatic can be obtained in the LaScO₃ host, including red, green, and blue emission with peak centered at 613, 544, and 428 nm, respectively. Therefore, two kinds of white light-emitting phosphors were obtained, LaScO₃:0.02Bi³⁺,0.05Tb³⁺,zEu³⁺ and LaScO₃:0.02Bi³⁺,0.03Eu³⁺,yTb³⁺. The energy transfer was characterized by decay times of the LaScO₃:xBi³⁺, yTb³⁺, zEu³⁺ phosphors. Moreover absolute internal QY and CIE chromatic coordinates are shown. The potential optical thermometry application of LaScO₃:Bi³⁺,Eu³⁺ was based on the temperature sensitivity of the fluorescence intensity ratio (FIR). The maximum S_a and S_r are 0.118 K⁻¹ (at 473.15 K) and 0.795% K⁻¹ (at 448.15 K), respectively. Hence, the LaScO₃:Bi³⁺,Eu³⁺ phosphor is a good material for optical temperature sensing.     

2,2,3-三氯-3-苯基-3-(3-甲基苯甲酰基)丙腈的合成研究

以苯甲酰氯、四氯化碳、间甲基苯甲酰氰为原料,合成了标题化合物。重点考察了氰化过程中不同原料配比、反应温度、时间、溶剂和催化剂用量对收率的影响。实验结果表明,其最佳反应条件为:n(1,1,2-三氯-2-苯基乙烯)∶n(3-甲基苯甲酰氰)=1∶1.2,二氯甲烷为反应溶剂,3 mmol催化剂三乙胺,室温反应5 h,总收率达80.6%。     

3-溴甲基-3-甲基氧杂环丁烷的合成

以2,2-二溴甲基丙醇(BBMP)为初始原料,通过与碱发生关环反应生成3-溴甲基-3-甲基氧杂环丁烷(BrMMO).讨论了碱的种类和用量对BBMP关环产率的影响以及反应体系中碱的浓度、反应温度和反应时间对合成BrMMO产率的影响.通过实验确定的最佳工艺条件为:BBMP与NaOH摩尔比为1.0∶1.1,NaOH醇溶液的质量分数为12%,反应温度为78℃,反应时间为4 h时,BrMMO产率为65%.最终产品经元素分析、IR和1HNMR检测确定为BrMMO.该试验工艺简单,原料易得,且溶剂便于回收、污染小.     

The Preparation and Crystal Structure of TlMnCl3, TlFeCl3, TlCoCl3 and TlNiCl3

The compounds TlMnCl₃, TlFeCl₃, TlCoCl₃ and TlNiCl₃ were prepared by heating T1C1 with the corresponding transition metal dichloride in an evacuated ampoule. Atomic positions were determined from powder photographs. All four compounds were found to be related to the perovskite type structure. TlMnCl₃ has a cubic structure, space group Pm3m, with a_o = 5.025 Å. The other three compounds are hexagonal, probable space group P6₃mc, with cell dimensions (in Å) a₀ = 6.976 and c₀ = 6.008 for the Fe compound, a₀ = 6.907 and c₀ = 5.981 for the Co compound and a₀ = 6.863 and c₀ = 5.881 for the Ni compound. The three hexagonal compounds are isomorphous. A measureable concentration of basal plane stacking faults was found to occur in TlFeCl₃ and also, to a lesser degree, in TlCoCl_3.     

Ba3Tb(BO3)3:Eu3+的制备与发光性质

采用高温固相法合成了Ba3Tb(BO3)3:Eu3+红色荧光粉,并研究了Ba3Tb(BO3)3:Eu3+的发光特性。Ba3Tb(BO3)3:Eu3+的激发光谱包含250nm～330nm和350nm～400nm的2个宽带,最大峰值位于383nm,可以被紫外-近紫外发光二极管(light-emitting diodes,LED)有效激发。Ba3Tb(BO3)3:Eu3+的发射谱显示出4组发射峰,其主发射峰位于620nm,对应Eu3+的5D0→7F2跃迁;Eu3+掺杂摩尔分数为2%时,Ba3Tb(BO3)3:Eu3+发光亮度最高。经分析发现Ba3Tb(BO3)3:Eu3+存在Tb3+→Eu3+的能量传递。     

Thermal analyses of poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)

Thermal analyses of poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(HB–HV)], and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(HB–HHx)] were made with thermogravimetry and differential scanning calorimetry (DSC). In the thermal degradation of PHB, the onset of weight loss occurred at the temperature (°C) given by T_o = 0.75B + 311, where B represents the heating rate (°C/min). The temperature at which the weight-loss rate was at a maximum was T_p = 0.91B + 320, and the temperature at which degradation was completed was T_f = 1.00B + 325. In the thermal degradation of P(HB–HV) (70:30), T_o = 0.96B + 308, T_p = 0.99B + 320, and T_f = 1.09B + 325. In the thermal degradation of P(HB–HHx) (85:15), T_o = 1.11B + 305, T_p = 1.10B + 319, and T_f = 1.16B + 325. The derivative thermogravimetry curves of PHB, P(HB–HV), and P(HB–HHx) confirmed only one weight-loss step change. The incorporation of 30 mol % 3-hydroxyvalerate (HV) and 15 mol % 3-hydroxyhexanoate (HHx) components into the polyester increased the various thermal temperatures T_o, T_p, and T_f relative to those of PHB by 3–12°C (measured at B = 40°C/min). DSC measurements showed that the incorporation of HV and HHx decreased the melting temperature relative to that of PHB by 70°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 90–98, 2001