含氮杂环、羧酸V型配体MOFs的合成及结构表征
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摘要
金属有机框架材料(MOFs)是一类由中心金属原子和有机配体构成的一类新型功能材料,通过有机配体的设计,金属离子的选择可以构筑出具有不同拓扑结构、不同性能的配位聚合物,从而使这一类化合物在生物活性、医药、光学材料、催化、吸附、气体存储等多方面有潜在的应用研究价值。
本文为了得到大孔洞材料为目的设计合成了8种具有V型框架结构的配体:(1)9,9'-二(4-羧酸苯基)芴(L1);(2)1,1'-二(4-羧酸苯基)环己烷(L1');(3)9,9'-二(4-(1H-四氮唑-5-)苯基)芴(L2);(4)9,9'-二(4-磷酸苯基)芴(L3);(5)1,1'-二(4-磷酸苯基)环己烷(L3-);(6)9,9'-二(4-(1-咪唑基)苯基)芴(L4);(7)9,9'-二(4-(1-1,2,3三氮唑基)苯基)芴(L5);(8)9,9'-二(4-(1-1,2,4三氮唑基)苯基)芴(L6)。对每一种配体都用NMR技术进行了表征。
本文通过溶剂热的方法,利用配体L1和配体L1′同Zn(NO_3)_2·6H_2O、Cu(NO_3)_2·3H_2O、Co(NO_3)_2·6H_2O三种金属盐合成了5种配位聚合物: (1)[Cu(L1)(DMF)]_n ;(2)[Zn(L1)(H_2O)]_n;(3)[Co(L1)(DMF)]_n;(4)[Cu(L1′)(DEF)]_n;(5)[Zn(L1′)(DMF)]_n,其中配合物(1)-(3)是配体L1的配合物,配合物(4)~(5)是配体L1-的配合物。在对反应条件进行系统考察之后,得到了最优合成路线:
配合物(1)最优合成路线:nL1:nCu(NO3)2-3H2O=1:1,溶剂选用DMF和甲醇,其体积比:VDMF:VCH3OH=1:1,反应温度115℃,反应时间4天,蓝色块状晶体,产率41.1%;
配合物(2)、(3)的最优合成路线:nL1:nZn(NO3)2-6H2O(nL1:nCo(NO3)2-6H2O)=3:1,溶剂选用DMF,反应温度90℃,反应时间3天,分别获得无色透明块状晶体和深绿色块状透明晶体,产率:51.3%和约100%。
配合物(4)的最优合成路线:nL1-:nCu(NO3)2-3H2O=3:1,溶剂选用DEF和H_2O,其体积比:VDEF:VH2O=3:1,反应温度90℃,反应时间3天,得到蓝色透明锥状晶体,产率45%。
配合物(5)的最优合成路线:n_(L1)-:n_(Zn(NO3)2-6H2O)=3:1,溶剂DMF,反应温度90℃,反应时间3天,得无色透明块状晶体,产率69%。
对每一种配位聚合物都用X-射线单晶衍射和热重分析(TGA)技术进行了表征。
通过对这5种配合物的配位环境及空间堆积模式的分析可知:在这5种配位聚合物中,配合物(1)~(4)具有相同的配位模式,金属离子都是6配位的变形八面体模式,配体中羧酸根采取顺-顺二齿配位模式,而配合物(5)的金属离子采取五配位模式,而配体羧酸根则采取反-反二齿配位和螯合配位两种模式。从5种配位聚合物的堆积图可以看出,配合物(1)~(3)形成了二维结构,在堆积结构中存在左右两种螺旋结构,而配合物(4)和(5)则形成一维链状结构,链中存在简单的空洞结构。
从配合物热重分析结果来看,这些配合物都发生了两个阶段的重量损失,配合物(1):261.8℃?386℃(失DMF),386℃?595℃(结构坍塌);配合物(2):125℃?211℃(失H2O),211℃?500℃(结构坍塌);配合物(3):180℃?311℃(失DMF),311℃?505℃(结构坍塌);配合物(4):227℃?267℃(失DEF),267℃?511℃(结构坍塌);配合物(5):186℃?276℃(失DMF),276℃?530℃(结构坍塌);从数据中我们可以看出,在空间形成二维结构的配合物(1)、(3)热稳定性要比在空间形成一维结构的配合物(4)、(5)好,配合物(1)、(3)的结构被破坏的温度都在300℃以上,而配合物(4)、(5)的结构破坏温度在250℃?300℃之间,配合物(2)虽然也形成了二维结构,但是由于结构骨架中含有H2O分子,从而导致了其失水温度和结构坍塌温度都较低。
Organic metal frame materials (MOFs) are a new type of porous materials, which are composed by central metal atoms and organic ligands. Through the design of organic ligand and the choice of metal ions, coordination polymers with different topology structure and properties could be built. This makes this sort of polymer compounds have potential applications in biological activity, medicine, optical materials, catalysis, adsorption, gas storage aspects.
Based on the purpose of obtaining several kinds of material with big pores, eight v-type frame structure ligands were designed and synthesized: (1) 9,9′-Bis(4-carboxylic acid phenyl) fluorine (L1); (2) 1,1′-Bis(4-carboxylic acid phenyl) cyclohexane (L1′); (3) 9,9′-Bis (4-1-H-tetrazylphenyl) fluorine (L2); (4) 9,9′-Bis(4-phosphoric acid phenyl) fluorine (L3); (5) 1,1′-Bis(4-phosphoric acid phenyl) cyclohexane (L3′); (6) 9,9′-Bis(4-1-imidazolyl phenyl) fluorine(L4); (7) 9,9′-Bis(4-1,2,3-triazolylphenyl)fluorine(L5); (8) 9,9′-Bis (4-1,2,4-triazolyl phenyl) fluorene. For every kind of ligands were characterized by NMR.
In this article, through solvent hot method, by using ligand L1 and ligand L1? with three metal salt of Zn(NO_3)_2·6H_2O, Cu(NO_3)_2·3H_2O, Co(NO_3)_2·6H_2O. Five coordination polymers were produced: (1) [Cu(L1)(DMF)]_n; (2) [Zn(L1)(H_2O)]_n; (3) [Co(L1)(DMF)]_n; (4) [Cu(L1′)(DEF)]_n; (5) [Zn(L1′)(DMF)]_n. In these complexes, complexes (1)~(3) were produced by the ligand L1, and complexes (4)?(5) were produced by ligand L1?, the optimal synthetic route was discovered after the reaction condition was investigated.
The optimal synthetic route of coordination polymer (1) was followed: 1 molar ratio of L1 and Cu (NO_3)_2·3H)_2O. DMF and CH_3OH were used as the solvents, the volume ratio of them was 1:1, reaction temperature was 115℃, time was four days. Then obtained the blue block crystal, the yield was 41.1%.
The optimal synthetic route of coordination polymer (2) and (3) were followed: 3 molar ratio of L1 and Zn(NO_3)_2·6H_2O or L1 and Co(NO_3)_2·6H_2O. DMF were used as the solvents, reaction temperature was 90℃, time was three days. Then obtained the colorless transparent crystal and dark green crystals, the yields were 51.3 % (complexes (2)) and about 100 % (complexes (3)).
The optimal synthetic route of coordination polymer (4) was followed: 3 molar ratio of L1? and Cu(NO3)2?3H2O. DEF and H_2O were used as the solvents, the volume ratio of them is 3:1,reaction temperature was 90℃, time was three days. Then obtained the blue cone crystals, the yield was 45%.
The optimal synthetic route of coordination polymer (5) was followed: 3 molar ratio of L1? and Zn(NO3)2?6H2O. DMF were used as the solvents, reaction temperature was 90℃, time was three days. Then we obtained the colorless transparent crystals. The yield was 69%.
All of the five coordination polymers were investigated by XRD and thermogravimetric analysis (TGA) technology.
By analyzing these five kinds of complexes coordination environment and space accumulation patterns, we knew that: In these five kinds of the coordination polymers, complexes (1) ~ (4) have the same coordination model, the coordination number of the metal ions was six, which belonged to distorted octahedron mode, the carboxylic acid root of ligands took the model of cis-cis bidental. the coordination number of the metal ion of complexes (5) was five, the carboxylic acid root of ligands took the model of tris-tris bidental and chelating patterns. From the packing diagrams of the five complexes. we can see that the complexes (1) ~ (3) formed the two-dimensional structure, in which the ligand exsisted the left spiral and right spiral structure. and one-dimensional chain structure was formed by the complexes (4) and (5), in which only simple hole existed.
From the thermo gravimetric analysis results, we knew that two phases of weight loss were happened, coordination polymer (1): 261.8℃?386℃(DMF lost), 386℃?595℃(structure collapsed); coordination polymer (2): 125℃?211℃(H2O lost), 211℃?500℃(structure collapsed); polymer (3): 180℃?311℃(DMF lost) 311℃?505℃(structure collapsed); polymer (4): 227℃?267℃(DEF lost), 267℃?511℃(structure collapsed); polymer (5):186℃?276℃(DMF lost), 276℃?530℃( structure collapsed). From the data, we could see that the complexes (1) and (3) with two-dimensional structure in space had more thermal stability than the complexes (4) and (5) with one-dimensional structure. The destruction temperature of structure of complexes (1) and (3) was above 300℃; however the destruction temperature of structure of complexes (4) and (5) was from 250℃to 300℃. Although coordination polymers (2) also had two-dimensional structure, the water molecules existed in the structural frame. Which led to a lower temperature of water lost and structure collapse than the complexes (1) and (3).
本文为了得到大孔洞材料为目的设计合成了8种具有V型框架结构的配体:(1)9,9'-二(4-羧酸苯基)芴(L1);(2)1,1'-二(4-羧酸苯基)环己烷(L1');(3)9,9'-二(4-(1H-四氮唑-5-)苯基)芴(L2);(4)9,9'-二(4-磷酸苯基)芴(L3);(5)1,1'-二(4-磷酸苯基)环己烷(L3-);(6)9,9'-二(4-(1-咪唑基)苯基)芴(L4);(7)9,9'-二(4-(1-1,2,3三氮唑基)苯基)芴(L5);(8)9,9'-二(4-(1-1,2,4三氮唑基)苯基)芴(L6)。对每一种配体都用NMR技术进行了表征。
本文通过溶剂热的方法,利用配体L1和配体L1′同Zn(NO_3)_2·6H_2O、Cu(NO_3)_2·3H_2O、Co(NO_3)_2·6H_2O三种金属盐合成了5种配位聚合物: (1)[Cu(L1)(DMF)]_n ;(2)[Zn(L1)(H_2O)]_n;(3)[Co(L1)(DMF)]_n;(4)[Cu(L1′)(DEF)]_n;(5)[Zn(L1′)(DMF)]_n,其中配合物(1)-(3)是配体L1的配合物,配合物(4)~(5)是配体L1-的配合物。在对反应条件进行系统考察之后,得到了最优合成路线:
配合物(1)最优合成路线:nL1:nCu(NO3)2-3H2O=1:1,溶剂选用DMF和甲醇,其体积比:VDMF:VCH3OH=1:1,反应温度115℃,反应时间4天,蓝色块状晶体,产率41.1%;
配合物(2)、(3)的最优合成路线:nL1:nZn(NO3)2-6H2O(nL1:nCo(NO3)2-6H2O)=3:1,溶剂选用DMF,反应温度90℃,反应时间3天,分别获得无色透明块状晶体和深绿色块状透明晶体,产率:51.3%和约100%。
配合物(4)的最优合成路线:nL1-:nCu(NO3)2-3H2O=3:1,溶剂选用DEF和H_2O,其体积比:VDEF:VH2O=3:1,反应温度90℃,反应时间3天,得到蓝色透明锥状晶体,产率45%。
配合物(5)的最优合成路线:n_(L1)-:n_(Zn(NO3)2-6H2O)=3:1,溶剂DMF,反应温度90℃,反应时间3天,得无色透明块状晶体,产率69%。
对每一种配位聚合物都用X-射线单晶衍射和热重分析(TGA)技术进行了表征。
通过对这5种配合物的配位环境及空间堆积模式的分析可知:在这5种配位聚合物中,配合物(1)~(4)具有相同的配位模式,金属离子都是6配位的变形八面体模式,配体中羧酸根采取顺-顺二齿配位模式,而配合物(5)的金属离子采取五配位模式,而配体羧酸根则采取反-反二齿配位和螯合配位两种模式。从5种配位聚合物的堆积图可以看出,配合物(1)~(3)形成了二维结构,在堆积结构中存在左右两种螺旋结构,而配合物(4)和(5)则形成一维链状结构,链中存在简单的空洞结构。
从配合物热重分析结果来看,这些配合物都发生了两个阶段的重量损失,配合物(1):261.8℃?386℃(失DMF),386℃?595℃(结构坍塌);配合物(2):125℃?211℃(失H2O),211℃?500℃(结构坍塌);配合物(3):180℃?311℃(失DMF),311℃?505℃(结构坍塌);配合物(4):227℃?267℃(失DEF),267℃?511℃(结构坍塌);配合物(5):186℃?276℃(失DMF),276℃?530℃(结构坍塌);从数据中我们可以看出,在空间形成二维结构的配合物(1)、(3)热稳定性要比在空间形成一维结构的配合物(4)、(5)好,配合物(1)、(3)的结构被破坏的温度都在300℃以上,而配合物(4)、(5)的结构破坏温度在250℃?300℃之间,配合物(2)虽然也形成了二维结构,但是由于结构骨架中含有H2O分子,从而导致了其失水温度和结构坍塌温度都较低。
Organic metal frame materials (MOFs) are a new type of porous materials, which are composed by central metal atoms and organic ligands. Through the design of organic ligand and the choice of metal ions, coordination polymers with different topology structure and properties could be built. This makes this sort of polymer compounds have potential applications in biological activity, medicine, optical materials, catalysis, adsorption, gas storage aspects.
Based on the purpose of obtaining several kinds of material with big pores, eight v-type frame structure ligands were designed and synthesized: (1) 9,9′-Bis(4-carboxylic acid phenyl) fluorine (L1); (2) 1,1′-Bis(4-carboxylic acid phenyl) cyclohexane (L1′); (3) 9,9′-Bis (4-1-H-tetrazylphenyl) fluorine (L2); (4) 9,9′-Bis(4-phosphoric acid phenyl) fluorine (L3); (5) 1,1′-Bis(4-phosphoric acid phenyl) cyclohexane (L3′); (6) 9,9′-Bis(4-1-imidazolyl phenyl) fluorine(L4); (7) 9,9′-Bis(4-1,2,3-triazolylphenyl)fluorine(L5); (8) 9,9′-Bis (4-1,2,4-triazolyl phenyl) fluorene. For every kind of ligands were characterized by NMR.
In this article, through solvent hot method, by using ligand L1 and ligand L1? with three metal salt of Zn(NO_3)_2·6H_2O, Cu(NO_3)_2·3H_2O, Co(NO_3)_2·6H_2O. Five coordination polymers were produced: (1) [Cu(L1)(DMF)]_n; (2) [Zn(L1)(H_2O)]_n; (3) [Co(L1)(DMF)]_n; (4) [Cu(L1′)(DEF)]_n; (5) [Zn(L1′)(DMF)]_n. In these complexes, complexes (1)~(3) were produced by the ligand L1, and complexes (4)?(5) were produced by ligand L1?, the optimal synthetic route was discovered after the reaction condition was investigated.
The optimal synthetic route of coordination polymer (1) was followed: 1 molar ratio of L1 and Cu (NO_3)_2·3H)_2O. DMF and CH_3OH were used as the solvents, the volume ratio of them was 1:1, reaction temperature was 115℃, time was four days. Then obtained the blue block crystal, the yield was 41.1%.
The optimal synthetic route of coordination polymer (2) and (3) were followed: 3 molar ratio of L1 and Zn(NO_3)_2·6H_2O or L1 and Co(NO_3)_2·6H_2O. DMF were used as the solvents, reaction temperature was 90℃, time was three days. Then obtained the colorless transparent crystal and dark green crystals, the yields were 51.3 % (complexes (2)) and about 100 % (complexes (3)).
The optimal synthetic route of coordination polymer (4) was followed: 3 molar ratio of L1? and Cu(NO3)2?3H2O. DEF and H_2O were used as the solvents, the volume ratio of them is 3:1,reaction temperature was 90℃, time was three days. Then obtained the blue cone crystals, the yield was 45%.
The optimal synthetic route of coordination polymer (5) was followed: 3 molar ratio of L1? and Zn(NO3)2?6H2O. DMF were used as the solvents, reaction temperature was 90℃, time was three days. Then we obtained the colorless transparent crystals. The yield was 69%.
All of the five coordination polymers were investigated by XRD and thermogravimetric analysis (TGA) technology.
By analyzing these five kinds of complexes coordination environment and space accumulation patterns, we knew that: In these five kinds of the coordination polymers, complexes (1) ~ (4) have the same coordination model, the coordination number of the metal ions was six, which belonged to distorted octahedron mode, the carboxylic acid root of ligands took the model of cis-cis bidental. the coordination number of the metal ion of complexes (5) was five, the carboxylic acid root of ligands took the model of tris-tris bidental and chelating patterns. From the packing diagrams of the five complexes. we can see that the complexes (1) ~ (3) formed the two-dimensional structure, in which the ligand exsisted the left spiral and right spiral structure. and one-dimensional chain structure was formed by the complexes (4) and (5), in which only simple hole existed.
From the thermo gravimetric analysis results, we knew that two phases of weight loss were happened, coordination polymer (1): 261.8℃?386℃(DMF lost), 386℃?595℃(structure collapsed); coordination polymer (2): 125℃?211℃(H2O lost), 211℃?500℃(structure collapsed); polymer (3): 180℃?311℃(DMF lost) 311℃?505℃(structure collapsed); polymer (4): 227℃?267℃(DEF lost), 267℃?511℃(structure collapsed); polymer (5):186℃?276℃(DMF lost), 276℃?530℃( structure collapsed). From the data, we could see that the complexes (1) and (3) with two-dimensional structure in space had more thermal stability than the complexes (4) and (5) with one-dimensional structure. The destruction temperature of structure of complexes (1) and (3) was above 300℃; however the destruction temperature of structure of complexes (4) and (5) was from 250℃to 300℃. Although coordination polymers (2) also had two-dimensional structure, the water molecules existed in the structural frame. Which led to a lower temperature of water lost and structure collapse than the complexes (1) and (3).
引文
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