2,4-二氯苯甲酸与2,2′:6′,2″-三联吡啶单核三元稀土配合物的合成、晶体结构、热分解机理及热力学性质  

Synthesis, crystal structures, thermal decomposition mechanism and thermal properties of mononuclear ternry lanthanide complex with 2,4-dichlorobenzoic acid and 2,2′:6′,2″-terpyridine

作　　者：王叶[1,2] 靳成伟 任宁[3] 张建军[1,2] WANG Ye JIN ChengWei REN Ning ZHANG JianJun(Testing and Analysis Center, Hebei Normal University, Shijiazhuang 050024, China College of Chemistry ＆ Material Science, Hebei Normal University, Shijiazhuang 050024, China College of Chemical Engineering＆ Material, Handan University, Handan 056005, China)

机构地区：[1]河北师范大学分析测试中心,石家庄050024 [2]河北师范大学化学与材料科学院,石家庄050024 [3]邯郸学院化学化工与材料学院,邯郸056005

出　　处：《科学通报》2016年第28期3146-3154,共9页Chinese Science Bulletin

基　　金：国家自然科学基金(21473049);河北省自然科学基金(B2016205207)资助

摘　　要：在室温下,通过溶液沉淀合成法得到了一种新型的单核稀土配合物[Ho(2,4-DCl BA)_3(terpy)(H_2O)]·H_2O(2,4-DCl BA:2,4-二氯苯甲酸;terpy:2,2′:6′,2″-三联吡啶),并通过元素分析、X射线单晶衍射、X射线粉末衍射、红外光谱以及拉曼光谱的测定对配合物进行了表征.每个Ho^(3+)周围有9个配位原子,并且形成带帽的四方反棱柱体结构.每个结构单元通过氢键作用以及p-p堆积作用形成一维、二维、三维超分子结构.利用同步热分析红外联用技术(TG/DSC-FTIR)对配合物的热分解机理进行研究,并分析了逸出气体的三维红外图谱.利用差示扫描量热技术(DSC)测定了配合物的比热,采用最小二乘法将平均摩尔热容与折合温度进行拟合得到两者的多项式方程并结合热力学方程计算得到相对于标准参考温度298.15 K时的热力学函数值.根据非线性等转化率法研究了配合物第一步反应的热分解动力学.The study of lanthanide complexes combining with aromatic-carboxylic acids has attracted extensive attention, according to their diverse coordination types and fascinating properties. In addition, a wide variety of applications including gas separation and storage, non-linear optics, electroluminescent materials, luminescent bioprobes, and catalysis have been utilized as functional materials. Lanthanide cations have the unique optical, electrical, and magnetic properties. However, the properties can be changed and even improved to be applied to more wider fields through the interactions between lanthanide cations and carboxylic acid ligands. Therefore, we chosen 2,4-dichlorobenzoic acid（2,4-DCl HBA） as the main ligands, and 2,2′：6′,2″-terpyridine（terpy） as auxiliary ligands to validly sensitize the lanthanide metal ions to assemble one novel mononuclear lanthanide complex 2,4-DCl BA： 2,4-dichlorobenzoate; terpy： 2,2′：6′,2″-terpyridine（[Ho（2,4-DCl BA）3（terpy）（H2O）]·H2O）. We dissolve 2,4-DCl HBA（0.6 mmol） and terpy（0.2 mmol） in ethanol（95%） and adjust the solution at the p H of 5–7 with the prepared Na OH solution（1 mol/L）. Add the mixed ligands solution to Ln Cl3·6H2O（0.2 mmol） aqueous solution under stirring and deposit it for 12 h. The complex was structurally characterized by elemental analysis, single crystal, powder X-ray diffraction, Infrared spectra and Raman spectrometry. The results revealed that the diffraction peak of complex is almost in agreement with simulated data, showing that the structure of the powder of complex is similar with the pure crystal. The detailed IR-R spectra of complex shows the spectrum of complex is different from the two ligands, the stretching vibration peak at 1549 cm^-1 attributed to the C=N bonds in terpy takes place red shift to 1537 cm-1, The vC=O（1631 cm^-1） of free carboxylic acid ligand completely disappears in the spectra of the complex and appear two another new absorption peak at 1553 and 1437 cm^

关 键 词：稀土羧酸配合物 超分子结构 同步热分析联用 热分解机理 差示扫描量热 热力学 

分 类 号：O641.4[理学—物理化学]