本文選題：含吡啶基多羧酸 + 溶劑熱合成　； 參考：《內蒙古大學》2017年碩士論文

【摘要】：近些年來,配位聚合物因結構的獨特性和新穎性使其在非均相催化、分子或離子識別、分子磁體、熒光材料和非線性光學材料等諸多領域具有廣闊的應用前景,因此合理的設計和構筑配位聚合物依然是研究者們的科研熱點。本文以含吡啶基多羧酸和有機羧酸為配體,通過調節(jié)金屬鹽與配體比例、反應溫度及時間、溶劑組成等條件,在水熱、溶劑熱條件下進行自組裝合成了 15個稀土或過渡金屬配位聚合物,并對它們的結構和相關性質進行了研究。以4-(吡啶-3-氧基)-鄰苯二甲酸(H2ppda)為主配體,分別與對苯二甲酸(H2bdc)、聯(lián)苯二甲酸(H2pbdc)、草酸(H2C204)等輔助配體,在水/乙醇體系中,成功構筑了三個系列14例結構新穎的鑭系配合物。配合物均為二維層狀構型,未配位的醚鍵O原子活性位點存在于二維層中,由于輔助配體軸向長度的不同,所以形成了三種不同大小的平面網格,網格的大小分別為:5.981 × 11.387 A,6.031 × 15.667 A,6.263×6.041 A;二維層均通過分子間氫鍵構成三維超分子結構。三個系列配合物的Ln-O平均鍵長均隨著Ln(Ⅲ)離子半徑的減小而減小,體現(xiàn)了鑭系收縮效應。測試了配位聚合物1-14的熱重、紅外、元素分析和PXRD等性質;此外,發(fā)現(xiàn)3-Gd配合物離子之間具有鐵磁性相互作用;同時,對發(fā)光的配位聚合物1-2,4-5,7-8,10-11,13-14進行了熒光性質的測定;研究發(fā)現(xiàn),它們均表現(xiàn)出稀土的特征發(fā)射峰。其中配合物4-Tb不僅可以作為檢測痕量硝基苯(NB)的熒光探針,而且還可以選擇性檢測Fe3+和Cr2O72-離子;配合物9-Tb可以作為選擇性檢測Al3+離子和CO32-離子的雙功能熒光探針。利用X-射線光電子能譜、X-射線粉末衍射、紫外可見吸收光譜對熒光檢測的機理進行了較詳盡的研究,并且分別對硝基苯分子、一些金屬離子和無機陰離子不同的熒光探針機理進行了詳細的解釋和推斷。通過4-(2,2';6',2"-三吡啶)-4'-1,2-鄰苯二甲酸(H2tbda)配體合成了一個配位聚合物,其分子式為[Zn(tbda)]n(15),配合物15為一維鏈狀結構,通過π…π相互作用形成二維結構,研究了配合物15的熱穩(wěn)定性、紅外、元素分析、PXRD、熒光等性質。發(fā)現(xiàn)15具有很高的熱穩(wěn)定性。
[Abstract]:In recent years, coordination polymers have been widely used in heterogeneous catalysis, molecular or ion recognition, molecular magnets, fluorescent materials and nonlinear optical materials due to their unique structure and novelty. Therefore, rational design and construction of coordination polymers is still a hot research topic for researchers. In this paper, with pyridyl polycarboxylic acid and organic carboxylic acid as ligands, by adjusting the ratio of metal salt to ligand, reaction temperature and time, solvent composition, etc. Fifteen rare earth or transition metal coordination polymers were synthesized by solvothermal self-assembly and their structures and properties were studied. With 4- (pyridine-3-oxy) -phthalic acid (H2ppda) as the main ligand and terephthalic acid (H2bdc), biphenyl dicarboxylic acid (H2pbdc), oxalic acid (H2C204) as auxiliary ligands, three novel lanthanide complexes were successfully constructed in water / ethanol system. All the complexes are of two dimensional layered configuration. The active sites of O atoms of uncoordinated ether bonds exist in the two dimensional layers. Due to the different axial lengths of the auxiliary ligands, three kinds of planar grids of different sizes have been formed. The mesh size is 5.981 脳 11.387 An 6.031 脳 15.667 An 6.263 脳 6.041 A. Two-dimensional layer is composed of three-dimensional supramolecular structure by intermolecular hydrogen bonding. The average Ln-O bond length of the three series of complexes decreases with the decrease of Ln (鈪，

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