席夫堿構(gòu)筑的配位化合物的合成、結(jié)構(gòu)及性質(zhì)
發(fā)布時(shí)間:2018-06-14 18:50
本文選題:席夫堿配體 + 3d-4f; 參考:《內(nèi)蒙古大學(xué)》2017年碩士論文
【摘要】:本論文以席夫堿配位化合物的合成、結(jié)構(gòu)為主要研究?jī)?nèi)容。利用兩個(gè)主配體:五齒席夫堿H2L1[鄰香蘭素縮N-(2-羥乙基)乙二胺]和四齒席夫堿H2L2(鄰香蘭素縮鄰氨基苯酚),分別與過(guò)渡金屬鹽及稀土金屬鹽反應(yīng)獲得配合物1-16。合成過(guò)程中通過(guò)添加有機(jī)橋聯(lián)配體及改變反應(yīng)條件等方式,利用零維席夫堿配合物構(gòu)筑一維鏈狀結(jié)構(gòu),并對(duì)配體、配合物進(jìn)行了紅外光譜表征。對(duì)配合物3-5、10和11-16進(jìn)行了 X-射線單晶衍射測(cè)試,對(duì)配合物4、10和11-14進(jìn)行熱穩(wěn)定性分析,配合物12進(jìn)行了磁性測(cè)試。配合物的分子式如下:[Fe(HL~1)_2]Cl為風(fēng)車狀結(jié)構(gòu)的單核Fe配合物,分子間通過(guò)π-π堆積和氫鍵作用形成一維鏈狀超分子。配合物2為雙核Cu配位化合物,其結(jié)構(gòu)中的輔助配體bbi橋聯(lián)兩個(gè)[Cu-L]的部分,再通過(guò)分子間氫鍵作用形成了一維鏈狀超分子。配合物3-16是四核[Ni2Ln2]系列配位簇合物。配合物中,鎳離子Ni(Ⅱ)為[O5N]六配位,呈現(xiàn)扭曲八面體構(gòu)型;稀土離子Ln(Ⅲ)為[O7N]八配位扭曲的正方反棱柱多面體。鎳離子Ni(II)與稀土離子LnⅢ)由μ2-O或μ3-O橋聯(lián)形成[Ni2Ln206]缺陷立方烷結(jié)構(gòu)(或蝴蝶拓?fù)浣Y(jié)構(gòu))。通過(guò)選用含羧酸基團(tuán)的輔助配體、改變反應(yīng)條件,使單分子席夫堿配合物(3-10)通過(guò)陰離子調(diào)節(jié)使分子間形成氫鍵和π-π相互作用構(gòu)筑成一維鏈狀配位超分子(11-16)。磁性測(cè)試表明,配合物12中存在鐵磁性相互作用。實(shí)驗(yàn)過(guò)程中,輔助配體的競(jìng)爭(zhēng)作用、輔助配體對(duì)溶液體系酸堿度的貢獻(xiàn)以及反應(yīng)過(guò)程中反應(yīng)物的添加順序,均對(duì)晶體的結(jié)構(gòu)產(chǎn)生影響。
[Abstract]:In this thesis, the synthesis and structure of Schiff base coordination compounds are the main research contents. Two principal ligands, pentodentate Schiff base H2L1 and tetradentate Schiff base H2L2, reacted with transition metal salts and rare earth metal salts respectively to obtain complexes 1-16. One dimensional chain structure was constructed by adding organic bridged ligands and changing reaction conditions. The ligand and complexes were characterized by IR spectra. The complexes 3-5N10 and 11-16 were characterized by X-ray single crystal diffraction, the thermal stability of complexes 4N10 and 11-14 were analyzed, and the magnetic properties of complex 12 were tested. The molecular formula of the complexes is as follows: [Fehhl1 + 2] Cl is a mononuclear Fe complex with windmill structure, and the molecules form one-dimensional chain supramolecular by 蟺-蟺 stacking and hydrogen bond interaction. Complex 2 is a binuclear Cu coordination compound, in which the auxiliary ligand bbi bridges two [Cu-L] parts, and then forms one dimensional chain supramolecular by the interaction of hydrogen bonds between molecules. Complex 3-16 is a tetranuclear [Ni _ 2L _ n _ 2] coordination cluster. In the complexes, Ni (鈪,
本文編號(hào):2018603
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