含剛性羧酸配體配合物的結(jié)構(gòu)和性質(zhì)
發(fā)布時(shí)間：2018-08-28 15:05
【摘要】：配位聚合物具有新穎的結(jié)構(gòu)、獨(dú)特的性質(zhì),在發(fā)光、吸附分離、氣體儲(chǔ)存和非均相催化等許多領(lǐng)域的有著潛在的應(yīng)用價(jià)值,引起當(dāng)代化學(xué)家的興趣,成為當(dāng)代化學(xué)研究中的熱點(diǎn)領(lǐng)域之一。但是,合成具有特定拓?fù)浣Y(jié)構(gòu)的配位聚合物需要選取合適的配體、金屬中心和在特定的合成途徑下才可以得到,因此配位聚合物的設(shè)計(jì)和構(gòu)筑仍是當(dāng)前該領(lǐng)域的研究難點(diǎn)所在。羧酸類配體由于羧基氧可以提供多元化的配位方式和較強(qiáng)的配位鍵,一直以來被廣泛用于合成配位聚合物。而其中帶有苯環(huán)的羧酸配體具有剛性,更容易獲得帶有孔道的框架結(jié)構(gòu)穩(wěn)定的金屬有機(jī)框架材料,因此是近些年來被研究最多的配體之一。但是現(xiàn)在單一的配體越發(fā)不能滿足我們對(duì)于配合物結(jié)構(gòu)精確把握的要求,因此一系列混合的配體被應(yīng)用于同一反應(yīng)體系。通過不同長(zhǎng)度的連接體和多元化的配位方式,一類具有規(guī)律性的配位聚合物被成功合成出來,更為重要的是我們研究發(fā)現(xiàn)定量的輔助羧酸配體的存在可以起到準(zhǔn)確酸度調(diào)節(jié)的作用,有助于結(jié)構(gòu)新穎配位聚合物的合成�；谝陨戏治�,本論文選擇2,6-吡啶二羧酸(2,6-H2PDC)和2,5-二溴對(duì)苯二甲酸(2,5-H2Br2BDC)作為主羧酸配體,選擇3,5-吡啶二羧酸(3,5-H2PDC)、2-羥基丙酸(Lac)和溴乙酸(BrMA)作為輔助羧酸配體,兩兩混合后再分別與單一金屬或混合金屬反應(yīng)合成了十一種結(jié)構(gòu)新穎的配位聚合物,并對(duì)其結(jié)構(gòu)和性質(zhì)進(jìn)行了研究。本論文主要包括以下兩個(gè)方面的工作:1、使用混合羧酸配體2,6-H2PDC和3,5-H2PDC與三組不同的雙組份金屬鹽反應(yīng)合成了一個(gè)單金屬配位聚合物[Zn2(2,6-PDC)2] (1)和兩個(gè)混金配位聚合物[CaPb6(2,6-PDC)6]C12 (2)和[Mg1.5Ce(2,6-PDC)3(H20)3]·3.5H20 (3)。三個(gè)配合物共同的特點(diǎn)是均只含有單一羧酸配體2,6-H2PDC。上述的配合物中盡管配體3,5-H2PDC沒有參與反應(yīng),但是起到了酸度調(diào)節(jié)劑的作用。配合物另一重要的特點(diǎn)是其結(jié)構(gòu)均可視為由金屬-連接體次級(jí)構(gòu)建單元和金屬節(jié)點(diǎn)組成。配合物1具有sqI網(wǎng)絡(luò)結(jié)構(gòu),可視為由兩種不同的(4,4)拓?fù)浣Y(jié)構(gòu)的網(wǎng)絡(luò)構(gòu)成。一種二維網(wǎng)絡(luò)是由壓扁的四面體節(jié)點(diǎn)[Zn(2,6-PDC)2]2-金屬-連接體次級(jí)構(gòu)建單元和共享的五配位的Zn(Ⅱ)節(jié)點(diǎn)構(gòu)成;另一種網(wǎng)絡(luò)是由二聯(lián)的2,6-PDC配體和四聯(lián)的Zn(Ⅱ)節(jié)點(diǎn)組成。配合物2是由18-聯(lián)的八面體[Ca(2,6-PDC)6]10-次級(jí)構(gòu)建單元和三聯(lián)的Pb(II)節(jié)點(diǎn)構(gòu)成,形成了一個(gè)雙節(jié)點(diǎn)的3, 18-聯(lián)的gez網(wǎng)絡(luò)。配合物3具有非常著名的4, 6-聯(lián)的stp網(wǎng)絡(luò)和一維三維1六角形納米孔道,它可視為由6-聯(lián)的三棱柱[Ce(2,6-PDC)3]3-金屬-連接體次級(jí)構(gòu)建單元和4-聯(lián)的Mg(II)構(gòu)成。此外,我們對(duì)配位聚合物1-3的熱穩(wěn)定性和固體熒光進(jìn)行了測(cè)試。基于配位聚合物3的納米孔道性質(zhì),我們考查了其對(duì)于碘分子的吸附和解吸性質(zhì)。研究發(fā)現(xiàn)每個(gè)分子單元能吸附約0.28 12,增重8.9%。但是,吸附碘分子以后,配位聚合物3的解析性能不好。2、使用剛性棒狀羧酸主配體2,5-H2Br2BDC和Lac、BrMA和3,5-H2PDC三種輔助羧酸配體與堿土金屬Ca、Ba,過渡金屬Fe、Zn,稀土金屬La、Eu和主族金屬Pb反應(yīng),通過溶劑熱和常溫?fù)]發(fā)的方法得到了八個(gè)配位聚合物。其中八個(gè)配位聚合物中只含有2,5-H2Br2BDC,這一結(jié)果表明三種輔助羧酸配體可能也只起到了條件調(diào)節(jié)pH值得作用。使用乳酸作為輔助羧酸配體,得到了四個(gè)配合物[Zn(Br2BDC)(DMF)] (4) 、 [Fe2(Br2BDC)2(DMF)3] (5)、[Ba(Br2BDC)(DMF)(H20)] (6)、[Pb(Br2BDC)(DMF)] (7)。配合物 4 是由梯形鏈在平行的ab面內(nèi)以…ABAB…的排列方式形成的二維網(wǎng)狀結(jié)構(gòu)。配合物5是由一維的方形孔道和41螺旋鏈通過共享金屬節(jié)點(diǎn)構(gòu)成的具有三種類型孔道的三維框架結(jié)構(gòu)。配合物6是一種具有pcu拓?fù)涞娜S金屬有機(jī)框架結(jié)構(gòu)。配合物7是由磚墻型二維網(wǎng)通過Br2BDC配體作為支柱構(gòu)成的三維框架結(jié)構(gòu)。使用溴乙酸作為輔助配體,得到了三個(gè)配體物[Ba2(HBr2BDC)2(Br2BDC)(DMF)2(H2O)2] (8)、[La2(Br2BDC)3(DMF)4(H2O)2] (9)和[Eu2(Br2BDC)3(DMF)2(H2O)2]·2DMF (10)。配位8是一種沿a軸方向有兩種一維孔道的三維框架結(jié)構(gòu)。配位9和10的結(jié)構(gòu)是類似的,都是由雙核金屬作為節(jié)點(diǎn)沿著b軸方向存在一維孔道的金屬有機(jī)框架。使用剛性3,5-吡啶二甲酸作為輔助配體只得到了配合物[Ca2(Br2BDC)2(DMF)2(H2O)2](11)。配合物11的結(jié)構(gòu)是一種兩重的自互穿的nbo型的三維框架結(jié)構(gòu)。上述結(jié)果表明Br2BDC配體的多樣橋聯(lián)模式有助于結(jié)構(gòu)多樣配合物的構(gòu)建。
[Abstract]:Coordination polymers have novel structures, unique properties and potential applications in many fields, such as luminescence, adsorption separation, gas storage and heterogeneous catalysis. They have attracted the interest of modern chemists and become one of the hotspots in contemporary chemical research. However, the synthesis of coordination polymers with specific topological structures needs to be selected. Suitable ligands, metal centers, and specific synthetic routes are available. Therefore, the design and construction of coordination polymers are still difficult in this field. Carboxylic acid ligands have been widely used in the synthesis of coordination polymers because of their various coordination modes and strong coordination bonds provided by carboxyl oxygen. Carboxylic acid ligands with phenyl rings in them are rigid and easy to obtain stable metal-organic frameworks with porous structures, so they are one of the most studied ligands in recent years. However, single ligands are increasingly unable to meet our requirements for accurate grasp of the structure of the complexes, so a series of mixed ligands are prepared. Apply to the same reaction system. Through different lengths of ligands and diversified coordination methods, a kind of coordination polymers with regularity are successfully synthesized. More importantly, we found that the existence of quantitative auxiliary carboxylic acid ligands can play an accurate acidity regulation role, which is conducive to novel coordination polymers. Based on the above analysis, 2,6-pyridine dicarboxylic acid (2,6-H2PDC) and 2,5-dibromoterephthalic acid (2,5-H2Br2BDC) were selected as the main carboxylic acid ligands, 3,5-pyridine dicarboxylic acid (3,5-H2PDC), 2-hydroxypropionic acid (Lac) and bromoacetic acid (BrMA) were selected as auxiliary carboxylic acid ligands, and then mixed with a single metal or mixed metal respectively. Eleven novel coordination polymers have been synthesized and their structures and properties have been studied. The main work of this paper is as follows: 1. A single metal coordination polymer [Zn2 (2,6-PDC) 2] (1) and two mixed gold have been synthesized by the reaction of mixed carboxylic acid ligands 2,6-H2PDC and 3,5-H2PDC with three different groups of two-component metal salts. The coordination polymers [CaPb6(2,6-PDC)6] C12(2) and [Mg1.5Ce(2,6-PDC)3(H20)3].3.5H20(3). The common feature of the three complexes is that they all contain only a single carboxylic acid ligand 2,6-H2PDC. Although the ligands 3,5-H2PDC do not participate in the reaction, they act as acidity regulators. Another important characteristic of the complexes is that they all have structures. Complex 1 has a sqI network structure and can be viewed as a network of two different (4,4) topologies. A two-dimensional network consists of flattened tetrahedral nodes [Zn(2,6-PDC)2] 2-metal-connector secondary construction units and shared five-coordinated Zn(II) nodes. Complex 2 is composed of 18-linked octahedron [Ca(2,6-PDC)6] 10-secondary construction unit and three-linked Pb(II) nodes, forming a two-node 3,18-linked Gez network. Complex 3 has a very famous 4,6-linked STP network and one-dimensional three-dimensional one-hexahexahedron network. In addition, we tested the thermal stability and solid fluorescence of the coordination polymer 1-3. Based on the properties of the nanochannels of the coordination polymer 3, we examined its adsorption and dissolution of iodine molecules. Absorption properties. It was found that each molecular unit could absorb about 0.2812, with an increase of 8.9%. However, after the adsorption of iodine molecule, the analytical performance of coordination polymer 3 was poor. 2. Three auxiliary carboxylic acid ligands, 2,5-H2Br2BDC and Lac, BrMA and 3,5-H2PDC, were used to assist the carboxylic acid ligands with alkaline earth metals Ca, Ba, transition metal Fe, Zn, rare earth metals La, Eu and main group. Eight coordination polymers were synthesized by solvothermal and ambient temperature evaporation of metal Pb. Only 2,5-H2Br2BDC was found in eight of the coordination polymers. The results show that the three auxiliary carboxylic acid ligands may also play a role in conditioning pH. Four complexes [Zn (Br2BDC) were obtained by using lactic acid as auxiliary carboxylic acid ligand. (DMF)] (4, [Fe2 (Br2BDC) 2 (DMF) 3] (5), [Ba (Br2BDC) (DMF) (H20)] (6), [Pb (Br2BDC) (DMF)] (7). Complex 4 consists of a trapezoidal chain in a parallel ab plane with a uuuuuuuuuuu ABAB... Complex 5 is a three-dimensional framework consisting of one-dimensional square channels and 41 helical chains through shared metal nodes. Complex 6 is a three-dimensional metal-organic framework with a PCU topology. Complex 7 is a brick-wall two-dimensional network through a Br2BDC ligand. Three ligands [Ba2 (HBr2BDC) 2 (Br2BDC) (DMF) 2 (H2O) 2] (8), [La2 (Br2BDC) 3 (DMF) 4 (H2O) 2] (9) and [Eu2 (Br2BDC) 3 (DMF) 2 (H2O) 2 (10)] were obtained by using bromoacetic acid as an auxiliary ligand. Similarly, all of the metal-organic frameworks with one-dimensional channels along the b-axis are composed of Binuclear metals. Only the complex [Ca2 (Br2BDC) 2 (DMF) 2 (H2O) 2] (11) was obtained by using a rigid 3,5-pyridinedicarboxylic acid as an auxiliary ligand. The structure of complex 11 is a double self-penetrating nbo-like three-dimensional framework. The diverse bridging patterns of BDC ligands contribute to the construction of diverse structural complexes.
【學(xué)位授予單位】：山東科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4
本文編號(hào)：2209744
[Abstract]:Coordination polymers have novel structures, unique properties and potential applications in many fields, such as luminescence, adsorption separation, gas storage and heterogeneous catalysis. They have attracted the interest of modern chemists and become one of the hotspots in contemporary chemical research. However, the synthesis of coordination polymers with specific topological structures needs to be selected. Suitable ligands, metal centers, and specific synthetic routes are available. Therefore, the design and construction of coordination polymers are still difficult in this field. Carboxylic acid ligands have been widely used in the synthesis of coordination polymers because of their various coordination modes and strong coordination bonds provided by carboxyl oxygen. Carboxylic acid ligands with phenyl rings in them are rigid and easy to obtain stable metal-organic frameworks with porous structures, so they are one of the most studied ligands in recent years. However, single ligands are increasingly unable to meet our requirements for accurate grasp of the structure of the complexes, so a series of mixed ligands are prepared. Apply to the same reaction system. Through different lengths of ligands and diversified coordination methods, a kind of coordination polymers with regularity are successfully synthesized. More importantly, we found that the existence of quantitative auxiliary carboxylic acid ligands can play an accurate acidity regulation role, which is conducive to novel coordination polymers. Based on the above analysis, 2,6-pyridine dicarboxylic acid (2,6-H2PDC) and 2,5-dibromoterephthalic acid (2,5-H2Br2BDC) were selected as the main carboxylic acid ligands, 3,5-pyridine dicarboxylic acid (3,5-H2PDC), 2-hydroxypropionic acid (Lac) and bromoacetic acid (BrMA) were selected as auxiliary carboxylic acid ligands, and then mixed with a single metal or mixed metal respectively. Eleven novel coordination polymers have been synthesized and their structures and properties have been studied. The main work of this paper is as follows: 1. A single metal coordination polymer [Zn2 (2,6-PDC) 2] (1) and two mixed gold have been synthesized by the reaction of mixed carboxylic acid ligands 2,6-H2PDC and 3,5-H2PDC with three different groups of two-component metal salts. The coordination polymers [CaPb6(2,6-PDC)6] C12(2) and [Mg1.5Ce(2,6-PDC)3(H20)3].3.5H20(3). The common feature of the three complexes is that they all contain only a single carboxylic acid ligand 2,6-H2PDC. Although the ligands 3,5-H2PDC do not participate in the reaction, they act as acidity regulators. Another important characteristic of the complexes is that they all have structures. Complex 1 has a sqI network structure and can be viewed as a network of two different (4,4) topologies. A two-dimensional network consists of flattened tetrahedral nodes [Zn(2,6-PDC)2] 2-metal-connector secondary construction units and shared five-coordinated Zn(II) nodes. Complex 2 is composed of 18-linked octahedron [Ca(2,6-PDC)6] 10-secondary construction unit and three-linked Pb(II) nodes, forming a two-node 3,18-linked Gez network. Complex 3 has a very famous 4,6-linked STP network and one-dimensional three-dimensional one-hexahexahedron network. In addition, we tested the thermal stability and solid fluorescence of the coordination polymer 1-3. Based on the properties of the nanochannels of the coordination polymer 3, we examined its adsorption and dissolution of iodine molecules. Absorption properties. It was found that each molecular unit could absorb about 0.2812, with an increase of 8.9%. However, after the adsorption of iodine molecule, the analytical performance of coordination polymer 3 was poor. 2. Three auxiliary carboxylic acid ligands, 2,5-H2Br2BDC and Lac, BrMA and 3,5-H2PDC, were used to assist the carboxylic acid ligands with alkaline earth metals Ca, Ba, transition metal Fe, Zn, rare earth metals La, Eu and main group. Eight coordination polymers were synthesized by solvothermal and ambient temperature evaporation of metal Pb. Only 2,5-H2Br2BDC was found in eight of the coordination polymers. The results show that the three auxiliary carboxylic acid ligands may also play a role in conditioning pH. Four complexes [Zn (Br2BDC) were obtained by using lactic acid as auxiliary carboxylic acid ligand. (DMF)] (4, [Fe2 (Br2BDC) 2 (DMF) 3] (5), [Ba (Br2BDC) (DMF) (H20)] (6), [Pb (Br2BDC) (DMF)] (7). Complex 4 consists of a trapezoidal chain in a parallel ab plane with a uuuuuuuuuuu ABAB... Complex 5 is a three-dimensional framework consisting of one-dimensional square channels and 41 helical chains through shared metal nodes. Complex 6 is a three-dimensional metal-organic framework with a PCU topology. Complex 7 is a brick-wall two-dimensional network through a Br2BDC ligand. Three ligands [Ba2 (HBr2BDC) 2 (Br2BDC) (DMF) 2 (H2O) 2] (8), [La2 (Br2BDC) 3 (DMF) 4 (H2O) 2] (9) and [Eu2 (Br2BDC) 3 (DMF) 2 (H2O) 2 (10)] were obtained by using bromoacetic acid as an auxiliary ligand. Similarly, all of the metal-organic frameworks with one-dimensional channels along the b-axis are composed of Binuclear metals. Only the complex [Ca2 (Br2BDC) 2 (DMF) 2 (H2O) 2] (11) was obtained by using a rigid 3,5-pyridinedicarboxylic acid as an auxiliary ligand. The structure of complex 11 is a double self-penetrating nbo-like three-dimensional framework. The diverse bridging patterns of BDC ligands contribute to the construction of diverse structural complexes.
【學(xué)位授予單位】：山東科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4
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