Syntheses and applications of Eu（Ⅲ） complexes of 2-thienyltrifluoroacetonate, terephthalic acid and phenanthroline as light conversion agents

A series of europium(Ⅲ) complexes of 2-thienyltrifluoroacetonate (HTTA), terephthalic acid (TPA) and phenanthroline (Phen) were synthesized. The new complexes Eu(TPA)(TTA)Phen and Eu2(TPA)(TTA)4Phen2 were characterized by elemental analysis, IR spectrum, scanning electron microscope and thermal stability analysis. The results show that the thermal stability of the Eu( Ⅲ ) complexes increases in the following order: the mononuclear complex Eu(TTA)3Phen, the binuclear complex Eu2(TPA)(TTA)4Phen2, the chain polynuclear complex Eu(TPA)(TTA)Phen. And the formation of the binuclear/polynuclear structure of the new complexes appears to be responsible for the enhancement of their thermal and optical stability. In addition, The fluorescence excitation spectra of these new complexes show more broad excitation bands than that of the complex Eu(TTA)3Phen corresponding to their formation. The enhancement of Eu3 fluorescence in the new complexes can be observed by the addition of Gd3 . The bright red luminescent plastics can be obtained when the complex EuGd(TPA)(TTA)4Phen2 is added above 0.5% (mass fraction).     

Synthesis and adsorption properties for Au（Ⅲ） of alkoxycarbonyl thiourea resin

A novel alkoxycarbonyl thiourea resin（ATR） was synthesized by monomer polymerization of oxydiethane-2,1-diyl dicarbonisothiocyanatidate and polyethylene polyamine, and characterized by FT-IR. The adsorption properties of ATR were investigated by batch test. The adsorption capacities for Au（Ⅲ）, Ag（Ⅰ）, Cu（Ⅱ）, Zn（Ⅱ, Fe（Ⅲ）, Ca（ Ⅱ ） and Mg（ Ⅱ ） are 4.65, 4.40, 0.40, 0.90, 0.86, 0.0080 and 0.016 mmol/g, respectively, when the adsorption condition is as follows： contact time 24 h, temperature 30 ℃, initial concentration of Au（Ⅲ） 5.08 mmol/L and that of other metals 0.10 mol/L, and concentration of acid 1.0 mol/L. The adsorption capacity for Au（Ⅲ） increases with the increase of contact time, temperature and initial concentration of Au（Ⅲ）. The capacity after five adsorption-desorption cycles remains 90% that of the first time, and the separation factors of ATR for binary metal ion solutions are larger than 995, indicating that ATR is of good regeneration property and selectivity. XPS results show that the functional atoms of ATR supply electrons for Au and coordinate with Au during the adsorption.     

Synthesis and optophysical properties of blue-emitting iridium （Ⅲ） complex bearing oxadiazole-based picolinic acid derivative

An iridium (III) bis[(4,6-difluorophenyl)pyridinato-N, C²][6-(6′-(4″-(5‴-phenyl-1‴, 3‴, 4‴-oxadiazole- 2‴-yl) phenoxy) hexyloxy picolinate) was synthesized and characterized by ¹H NMR and elementary analysis in order to study the effect of ancillary ligand of the oxadiazole-based picolinic acid derivative on optophysical properties of its iridium complex, and further to obtain an iridium complex with highly-efficient blue emission. The thermal stability, UV absorption and photoluminescent properties of this iridium complex were investigated. Compared with iridium (III) bis[(4,6-difluorophenyl)pyridinato-N, C²](picolinate) reported as a highly-efficient blue electroluminescent material, this iridium complex bearing an oxadiazole-based picolinic acid derivative presents higher thermal stability, more intense UV absorption at 291 nm and similar photoluminescent spectrum peaked at 469 nm. This indicates that tuning ancillary ligand of picolinic acid with an oxadiazole unit can improve the optophysical properties of its iridium complex. Foundation item: Projects(20772101, 50473046) supported by the National Natural Science Foundation of China; Project(2007FJ3017) supported by the Hunan Provincial Science Foundation, China; Project(07C764) supported by the Science Foundation of the Education Department of Hunan Province, China     

2-(4,’6’-二甲氧基)嘧啶氧基-6-硝基-N-芳基苄胺衍生物的合成

以硫脲和丙二酸二乙酯为初始原料,经环合等多步反应合成4,6-二甲氧基-甲砜基嘧啶,间硝基邻甲基苯胺经重氮化得到重氮产物间硝基邻甲基苯酚.4,6-二甲氧基-甲砜基嘧啶和间硝基邻甲基苯酚反应得到2-(苄基-6-硝基-苯氧基)-4,’6’-二甲氧基嘧啶,再经溴化反应得到2-(苄基溴-6-硝基-苯氧基)-4,’6’-二甲氧基嘧啶,其与六个取代基苯胺反应,分别得到六个2-(4,’6’-二甲氧基)嘧啶氧基-6-硝基-N-芳基苄胺衍生物,产物经质谱和核磁氢谱检测确定.     

2-(4'''',6''''-二甲氧基)嘧啶氧基-6-硝基 -N-芳基苄胺衍生物的合成

以硫脲和丙二酸二乙酯为初始原料,经环合等多步反应合成4,6-二甲氧基-甲砜基嘧啶,间硝基邻甲基苯胺经重氮化得到重氮产物间硝基邻甲基苯酚.4,6-二甲氧基-甲砜基嘧啶和间硝基邻甲基苯酚反应得到2-(苄基-6-硝基-苯氧基)-4',6'-二甲氧基嘧啶,再经溴化反应得到2-(苄基溴-6-硝基-苯氧基)-4',6'-二甲氧基嘧啶,其与六个取代基苯胺反应,分别得到六个2-(4',6'-二甲氧基)嘧啶氧基-6-硝基-N-芳基苄胺衍生物,产物经质谱和核磁氢谱检测确定.     

Synthesis of 1,4-benzenedicarbonyl thiourea resins and their adsorption properties for Ag（I）

Several 1,4-benzenedicarbonyl thiourea resins (BTR) were synthesized through interfacial polymerization between 1,4-benzenedicarbonyl diisothiocyanate and polyamine. Their structures were confirmed by FT-IR. The adsorption properties (including the effect of adsorption time, pH, initial concentrations and temperature) of BTR-1, BTR-2 and BTR-3 for Ag(I) were investigated by batch tests. The results show that the adsorption equilibria of BTR-1, BTR-2, BTR-3 for Ag(I) are achieved after about 10 h. Their equilibrium adsorption capacities are 7.11, 6.75 and 6.23, respectively, and the adsorption process accords with G. E. Boyd equation and Langmuir adsorption isotherm as well. The adsorption capacities increase with the increase of pH (the highest uptake values are observed at pH being about 6–7). The thermodynamic parameters of BTR-1 were calculated. The results show that ΔH ^Θ; and ΔS ^Θ are 6 958.8 J/mol and 64.28 J/(mol·K), respectively, and ΔG ^Θ at 20, 30, 40 and 50 °C are −11.79, −12.52, −13.16 and −13.8 kJ/mol, respectively. The silver-loaded resins can be quantitatively eluted by a solution containing 6% thiourea in 1 mol/L HNO₃.     

Synthesis and fluorescence properties of Tb(Ⅲ) complexes with pyridine-2,6-dicarboxylic acid derivatives

Two novel ligands named 4-styrylpyridine-2,6-dicarboxylic acid (4-SPDA) and 4-(4-(2-(2, 6-dicarboxypyridin-4-yl)-vinyl)styryl)pyridine-2,6-dicarboxylic acid(DSPDA) and their complexes with Tb(Ⅲ) were synthesized and characterized by infrared spectrometry, 1H nuclear magnetic resonance, elemental analysis and gas chromatograph-mass spectrometry. The ligand synthetic route was optimized. The fluorescence properties of the complex in solid state, in different kind of solvents and in solutions with different pH values were investigated in detail. The results show that the yields of DSPDA and 4-SPDA reach over 78% by Wittig-Horner reaction and other eight pyridine-2, 6-dicarboxylic acid derivatives with different substituents on pyridine ring, and their complexes with Tb(Ⅲ) are also obtained. The fluorescence intensities of the complexes with electron-donating groups are more intense than those of the complexes with electron-withdrawing groups on pyridine ring; fluorescence intensities of the complexes are the strongest in neutral solution (pH=7), and the less the dipole moment of solvent molecule is, the stronger the fluorescence intensity is. It is found that the two ligands (4-APDA and DSPDA) are the good sensitizers for Tb(Ⅲ) ion.     

吡啶-2,6-二甲酸二丁酯的催化合成研究

采用分子筛HBEA负载杂多酸和杂多酸盐为催化剂,研究了吡啶-2,6-二甲酸（PDA）与正丁醇（n-BuOH）酯化合成吡啶-2,6-二甲酸二丁酯（PDADBE）.考察了不同催化剂活性以及反应原料配比、反应温度、反应时间等因素对于该酯化反应的催化的影响.实验结果表明,分子筛负载型催化剂HPW/HBEA对于催化酯化合成吡啶-2,6-二甲酸丁酯显示出良好的催化活性,在n（PDA）∶n（n-BuOH）=1∶30,催化剂用量为0.5 g（对3.44 g吡啶-2,6-二甲酸）,反应温度118℃,反应时间8 h的最佳工艺条件,收率达到93.5%.     

新显色剂BTACIPACA的合成及与铁显色反应研究

合成一种新的杂环不对称双偶氮变色酸 2 苯并噻唑偶氮 7 (4’ 氯苯偶氮 ) 1 ,8 二羟基萘 3 ,6 二磺酸 .研究在pH6.2 的邻苯二甲酸氢钾 氢氧化钠缓冲介质中显色试剂与Fe(III)的显色反应特性 .结果表明 :试剂与Fe(III)及CTMAB形成 2∶1∶1的三元络合物 ,显色反应 5min完全并至少可稳定 4h ,以试剂空白为参比络合物的最大吸收波长为 690nm ,表观摩尔吸光系数为 8.0 7× 1 0 4 L·mol- 1·cm- 1,质量浓度在 0～ 5 μg/2 5ml范围内符合比耳定律 ,用拟定的方法测定石灰石、高炉渣中Fe(III)的含量得到满意的结果 .     

过渡金属谷氨酸希夫碱配合物的合成及表征

利用模拟酶催化氧化的方法合成了五种谷氨酸希夫碱过渡金属配合物Mn(Glu -Sal)、Fe(Glu-Sal)、Co(Glu -Sal)、Ni(Glu -Sal)、Cu(Glu -Sal) ,对配合物进行了热重———差热分析、红外光谱分析、XPS分析 ,用ICP法测定了配合物的金属含量 ,配合物的结构分析与目标基本吻合。     

二亚磷酸二(2,6-二叔丁基对甲酚)季戊四醇酯的合成

以亚磷酸三乙酯、季戊四醇和2,6-二叔丁基对甲酚为原料合成了抗氧剂二亚磷酸二（2,6-二叔丁基对甲酚）季戊四醇酯。探讨了物料配比、催化剂的种类及用量、反应时间等反应条件对产率的影响,并通过正交试验法确定了最佳工艺条件。实验结果表明：催化剂为无水碳酸钾,其用量为0.6 g;物料配比（n（季戊四醇）∶n（亚磷酸三乙酯）∶n（2,6-二叔丁基苯酚））为1.0∶2.12∶2.04;反应Ⅰ温度为130~140℃,反应Ⅰ时间为2 h,反应Ⅱ温度为170~180℃,反应Ⅱ时间为4 h。在最佳工艺条件下所制得的产品为白色粉末状固体,熔点为67~69℃,产率为87%左右。此外,通过元素分析、红外光谱分析对产品进行了物性和结构表征。     

铕-镧-柠檬酸-1,10-菲咯啉配合物荧光性能研究

分别合成了铕与柠檬酸配位的二元配合物,铕、柠檬酸、1,10-菲咯啉配位的三元配合物和掺杂不同量镧的多核三元配合物.经过元素分析、红外分析和热重差热分析等手段确定了配合物的组成与结构.通过荧光光谱及荧光寿命测试了其荧光性能,结果表明当铕与镧掺杂摩尔比为6:4时能得到荧光强度最强且荧光寿命最长的稀土配合物.实验结果拟合表明,当铕镧摩尔比在1:9～5:5时,镧离子对铕荧光的敏化程度以指数形式衰减,当铕镧摩尔比在6:4～9:1时,镧离子对铕荧光的敏化程度以线性方式衰减.     

三脚架型配体、配合物的合成及荧光性质

为了进一步研究配体结构对稀土离子配位行为的影响,合成了以N为中心的三足配体——2,2′,2″-三（2-苯胺基甲酰基苯氧基）三乙胺（L）及其稀土硝酸盐配合物．试验表明,在合成三（2-氯乙基）胺盐酸盐时,应先用适当的溶剂（如苯）溶解三乙醇胺盐酸盐,然后向其中缓慢滴加氯化亚砜,并在合成N-苯基水杨酰胺的过程中,用DCC作脱水剂,效果较好．该合成方法明显降低了氯化亚砜的挥发,减少了原料损失,使操作条件更温和。收率可达80％以上：在室温下．铽配合物表现出Tb^3＋的特征荧光发射峰．