新型釩多酸基金屬有機多面體的結(jié)構(gòu)、自組裝合成和性能研究
發(fā)布時間：2018-07-29 05:50
【摘要】：金屬有機多面體(MOPs)是繼分子篩和金屬有機框架(MOFs)之后,又一類發(fā)展迅速的多孔材料。MOPs不是無限的三維網(wǎng)絡(luò)結(jié)構(gòu),而是孤立的分子實體;它們構(gòu)建于邊共享的分子多邊形或通過分子頂點之間的相互連接而成�；诮饘倥c有機配體自組裝形成的分子多面體,其具有納米尺度的籠形結(jié)構(gòu)以及內(nèi)、外表面積。同時,MOPs具有靈活的幾何拓撲,尺寸,表面積和孔性。它們可以作為主體分子,在許多領(lǐng)域具有重要的應(yīng)用,包括催化,吸附,生物物理學,還可以作為前驅(qū)體去構(gòu)建MOFs材料。多金屬釩酸鹽(POVs),作為多酸的一個獨特的分支,一直吸引人們的研究興趣,因為釩多酸不僅具有結(jié)構(gòu)多樣性和卓越的特性,而且它們在分子磁學,催化,氧化還原,醫(yī)學,生物活性材料等方面有潛在應(yīng)用。本論文選擇簡單的金屬釩源和不同的羧酸配體設(shè)計合成了13個釩多酸基金屬有機多面體。在特定的溶劑熱條件下,我們得到了新穎的具有不同配位模式的釩多酸基建筑塊,這對于MOPs的形成起到了關(guān)鍵作用。由于得到化合物的骨架中存在還原態(tài)的釩,我們對大部分化合物的磁性進行了探索。1.我們的策略是利用釩多酸和線型二羧酸配體構(gòu)建釩多酸基有機無機雜化材料。最終得到了三種同構(gòu)的基于金屬{V_5O_9Cl}單元的金屬有機八面體配位籠。通過單晶X射線衍射,粉末射線衍射,紅外,熱重以及N2吸附等手段對這些化合物進行了表征(NH_2Me_2)12[(V_5O_9Cl)6(BDC)12]·(DMF)17(1)(NH_2Me_2)12[(V_5O_9Cl)6(BDC-NH_2)12]·(DMF)14(2)(NH_2Me_2)12[(V_5O_9Cl)6(BDC-Br)12]·(DMF)8(3)BDC=1,4-對苯二甲酸BDC-NH_2=2-氨基-對苯二甲酸BDC-Br=2-溴-對苯二甲酸2.我們采用角形配體或尺寸加成的雙齒羧酸配體與釩氧簇自組裝,成功的獲得了三種新穎的釩多酸基金屬有機多面體;其結(jié)構(gòu)中都含有{V_5O_9Cl}建筑單元。有趣地是,由于配體性質(zhì)的不同,它們的結(jié)構(gòu)呈現(xiàn)差異性,包括截角三棱柱、截角四棱錐和截角八面體結(jié)構(gòu)。此外,磁性研究表明他們具有相似的鐵磁性行為。(NH_2Me_2)6[(V_5O_9Cl)3(TDA)6]·(DMF)1.5(CH3OH)0.5(4)(NH_2Me_2)8[(V_5O_9Cl)4(m-BDC)8]·(DMF)3(CH3OH)0.5(5)(NH_2Me_2)12[(V_5O_9Cl)6(NDC)12]·(DMF)8(CH3CH_2OH)0.5(6)TDA=噻吩-2,5-二羧酸m-H_2BDC=間苯二甲酸2,6-H_2NDC=2,6-萘二甲酸3.我們對五種新穎的烷氧基修飾的釩多酸基金屬有機多面體的溶劑熱合成、結(jié)構(gòu)進行了報道。同時,對其中三種化合物的磁性進行了研究;結(jié)果表明他們都具有反鐵磁性相互作用。據(jù)我們所知,此工作將烷氧基修飾的釩多酸引入到金屬有機材料當中,這是比較罕見的。{V6S}建筑單元的發(fā)現(xiàn)不僅為有限的釩多酸家族增加了一個典型的實例,而且它作為一個三連接的無機配體,適合與有機配體自組裝構(gòu)建截角四面體結(jié)構(gòu)或分子膠囊。(NH_2Et_2)8{[V6O6(OCH3)9(SO4)]4(BDC)6}(DEF)2(7)(NH_2Et_2)8{[V6O6(OCH3)9(SO4)]4(BDC-NH_2)6}(DEF)1.5(8)(NH_2Et_2)8{[V6O6(OCH3)9(SO4)]4(BDC-Br)6}(DEF)1(9)(NH_2Et_2)8{[V6O6(OCH3)9(SO4)]4(BTC)4}(DEF)0.5(10)(NH_2Et_2)8{[V6O6(OCH3)9(SO4)]4(BTB)4}(DEF)1.5(11)BTC=1,3,5-均苯三甲酸;BTB=1,3,5-三(4-羧基苯基)苯4.基于我們之前的工作,在相似的溶劑熱條件下,我們使用三氯化釩替換硫酸氧釩,得到了兩例含有新型{V_7}同多酸簇的釩基金屬有機多面體。他們呈現(xiàn)精美的截角四面體籠形結(jié)構(gòu)。此外,這種{V_7}多酸基建筑單元是首次被發(fā)現(xiàn),與文獻報道的釩基MOPs相比,其具有最高核數(shù)的釩氧簇。磁性研究表明他們具有相似的反鐵磁行為。(NH_2Et_2)4{[V6O6(OCH3)9(VO3)(H_2O)]4(BDC)6}(DEF)0.5(12)(NH_2Et_2)4{[V6O6(OCH3)9(VO3)(H_2O)]4(BDC-NH_2)6}(DEF)0.5(CH3OH)0.5(13)
[Abstract]:Metal organic polyhedron (MOPs) is followed by molecular sieves and metal organic frameworks (MOFs). Another fast developing porous material,.MOPs, is not an infinite three-dimensional network structure, but an isolated molecular entity; they are constructed of polygons shared by the side or interconnected through the top of the molecule. Based on metal and organic ligands The molecular polyhedron formed by self assembly has a nanoscale cage structure as well as inside, surface area. At the same time, MOPs has a flexible geometric topology, size, surface area and porosity. They can be used as the main molecules in many fields, including catalysis, adsorption, biophysics, and can be used as precursors to build MOFs. Material. Polymetallic vanadate (POVs), as a unique branch of polyacid, has attracted people's interest in research, because vanadate not only has structural diversity and excellent properties, but also has potential applications in molecular magnetism, catalysis, oxidation-reduction, medicine, bioactive material and so on. This paper chooses a simple metal vanadium source. 13 vanadium polyacid based polyhedron are designed and synthesized with different carboxylic ligands. Under specific solvent thermal conditions, we have obtained a novel vanadium polyacid base with different coordination modes, which plays a key role in the formation of MOPs. The magnetic properties of the compounds are explored.1. our strategy is to use vanadate and linear two carboxylic acid ligands for the construction of vanadium polyacid organic-inorganic hybrid materials. Finally, three isomorphic metal organic eight surface coordination cages based on metal {V_5O_9Cl} elements are obtained. By single crystal X ray diffraction, powder ray diffraction, infrared, thermo gravimetric and N2 absorption. NH_2Me_2 12[(V_5O_9Cl) 6 (BDC) 12]. (DMF) 17 (DMF) 17 (NH_2Me_2) 12[(NH_2Me_2) 12[(V_5O_9Cl) 6 (BDC-NH_2) 12] (BDC-NH_2) 14 (2) 6 (3) 8 (3) used angular ligands for benzoic acid terephthalic terephthalic terephthalic acid terephthalic terephthalic terephthalic acid (3). Three kinds of novel vanadium polyacid base metal polyhedron are successfully obtained by self assembly of the size addition dicarboxylic carboxylic ligands and vanadium oxygen clusters. The structure contains {V_5O_9Cl} building units. Interestingly, their structure is different because of the different ligand properties, including the truncated three prism, the truncated four pyramid and the truncated eight face structure. In addition, magnetic properties show that they have similar ferromagnetic behavior. (NH_2Me_2) 6[(V_5O_9Cl) 3 (TDA) 6]. (DMF) 1.5 (CH3OH) 0.5 (CH3OH) 0.5 (NH_2Me_2) 8[(V_5O_9Cl) 4 (m-BDC) 8]. 3 (8) 8 (6) 8 (6), 8 (6), 8 (6) Acid 3., we reported the structure of the solvothermal synthesis of five novel alkoxy modified vanadium polyhedron polyhedron. Meanwhile, the magnetic properties of three of these compounds were studied. The results show that they all have antiferromagnetic interaction. In organic materials, the discovery of this rare.{V6S} building unit is not only a typical example of a limited vanadate family, but also as a three connected inorganic ligand, suitable for the construction of a truncated tetrahedral structure or molecular capsule with organic ligand. (NH_2Et_2) 8{[V6O6 (OCH3) 9 (SO4)]4 (BDC) 6} (DEF) 2 (7) (N) (N) H_2Et_2) 8{[V6O6 (OCH3) 9 (SO4)]4 (BDC-NH_2) 6} (DEF) 1.5 (NH_2Et_2) 8{[V6O6 (OCH3) 9 (SO4) 1 (9) 0.5 (10) 9 (11) Under the solvothermal condition, we use three vanadium chloride to replace vanadium sulfate, and two cases of vanadium based metal organic polyhedron containing a new {V_7} polyacid cluster. They present a fine truncated tetrahedral cage structure. In addition, this {V_7} polyacid base building unit is first discovered, and is the highest compared with the reported vanadium base MOPs. Nuclear number of vanadium oxygen clusters. Magnetic studies show that they have similar antiferromagnetic behavior. (NH_2Et_2) 4{[V6O6 (OCH3) 9 (VO3) (H_2O)]4 (BDC) 6} (DEF) 0.5 (12) (NH_2Et_2) 4{[V6O6 (OCH3) 9 (OCH3) 0.5 (13) 0.5 (13)
【學位授予單位】：東北師范大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O641.4
[Abstract]:Metal organic polyhedron (MOPs) is followed by molecular sieves and metal organic frameworks (MOFs). Another fast developing porous material,.MOPs, is not an infinite three-dimensional network structure, but an isolated molecular entity; they are constructed of polygons shared by the side or interconnected through the top of the molecule. Based on metal and organic ligands The molecular polyhedron formed by self assembly has a nanoscale cage structure as well as inside, surface area. At the same time, MOPs has a flexible geometric topology, size, surface area and porosity. They can be used as the main molecules in many fields, including catalysis, adsorption, biophysics, and can be used as precursors to build MOFs. Material. Polymetallic vanadate (POVs), as a unique branch of polyacid, has attracted people's interest in research, because vanadate not only has structural diversity and excellent properties, but also has potential applications in molecular magnetism, catalysis, oxidation-reduction, medicine, bioactive material and so on. This paper chooses a simple metal vanadium source. 13 vanadium polyacid based polyhedron are designed and synthesized with different carboxylic ligands. Under specific solvent thermal conditions, we have obtained a novel vanadium polyacid base with different coordination modes, which plays a key role in the formation of MOPs. The magnetic properties of the compounds are explored.1. our strategy is to use vanadate and linear two carboxylic acid ligands for the construction of vanadium polyacid organic-inorganic hybrid materials. Finally, three isomorphic metal organic eight surface coordination cages based on metal {V_5O_9Cl} elements are obtained. By single crystal X ray diffraction, powder ray diffraction, infrared, thermo gravimetric and N2 absorption. NH_2Me_2 12[(V_5O_9Cl) 6 (BDC) 12]. (DMF) 17 (DMF) 17 (NH_2Me_2) 12[(NH_2Me_2) 12[(V_5O_9Cl) 6 (BDC-NH_2) 12] (BDC-NH_2) 14 (2) 6 (3) 8 (3) used angular ligands for benzoic acid terephthalic terephthalic terephthalic acid terephthalic terephthalic terephthalic acid (3). Three kinds of novel vanadium polyacid base metal polyhedron are successfully obtained by self assembly of the size addition dicarboxylic carboxylic ligands and vanadium oxygen clusters. The structure contains {V_5O_9Cl} building units. Interestingly, their structure is different because of the different ligand properties, including the truncated three prism, the truncated four pyramid and the truncated eight face structure. In addition, magnetic properties show that they have similar ferromagnetic behavior. (NH_2Me_2) 6[(V_5O_9Cl) 3 (TDA) 6]. (DMF) 1.5 (CH3OH) 0.5 (CH3OH) 0.5 (NH_2Me_2) 8[(V_5O_9Cl) 4 (m-BDC) 8]. 3 (8) 8 (6) 8 (6), 8 (6), 8 (6) Acid 3., we reported the structure of the solvothermal synthesis of five novel alkoxy modified vanadium polyhedron polyhedron. Meanwhile, the magnetic properties of three of these compounds were studied. The results show that they all have antiferromagnetic interaction. In organic materials, the discovery of this rare.{V6S} building unit is not only a typical example of a limited vanadate family, but also as a three connected inorganic ligand, suitable for the construction of a truncated tetrahedral structure or molecular capsule with organic ligand. (NH_2Et_2) 8{[V6O6 (OCH3) 9 (SO4)]4 (BDC) 6} (DEF) 2 (7) (N) (N) H_2Et_2) 8{[V6O6 (OCH3) 9 (SO4)]4 (BDC-NH_2) 6} (DEF) 1.5 (NH_2Et_2) 8{[V6O6 (OCH3) 9 (SO4) 1 (9) 0.5 (10) 9 (11) Under the solvothermal condition, we use three vanadium chloride to replace vanadium sulfate, and two cases of vanadium based metal organic polyhedron containing a new {V_7} polyacid cluster. They present a fine truncated tetrahedral cage structure. In addition, this {V_7} polyacid base building unit is first discovered, and is the highest compared with the reported vanadium base MOPs. Nuclear number of vanadium oxygen clusters. Magnetic studies show that they have similar antiferromagnetic behavior. (NH_2Et_2) 4{[V6O6 (OCH3) 9 (VO3) (H_2O)]4 (BDC) 6} (DEF) 0.5 (12) (NH_2Et_2) 4{[V6O6 (OCH3) 9 (OCH3) 0.5 (13) 0.5 (13)
【學位授予單位】：東北師范大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O641.4
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