基于芳香多羧酸或杂多酸的配位化合物的合成、结构与性质研究
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摘要
本论文以设计和开发结构新颖的有机-无机杂化物为目标，基于芳香多羧酸或杂多酸，利用水热合成技术合成了一系列新的化合物。从分子水平上探讨了配体的构型和反应条件对化合物结构的影响，总结合成规律。比较同系列化合物的性质差异。通过单晶X-射线衍射、元素分析、红外光谱分析和热稳定性对晶体结构进行表征，对化合物的荧光性质进行了初步研究。
1.以均苯四甲酸（H4bta）为有机配体，水热反应条件下合成了7个具有三维（3D）结构的稀土配位化合物。化合物5和6的结构中含有二维（2D）的金属-氧层，而化合物7的结构中含有一维（1D）的金属-氧链。首次报道了H4bta的三种新的配位模式。
[Pr(bta)0.5(H2bta)0.5(H2O)](1)
[Eu2(bta)1.5(H2O)2](2)
[Ln2(bta)1.5(H2O)4]3H2O (Ln=La(3), Ce(4))
[Ln2(bta)1.5(H2O)2] H2O (Ln=Ce(5), Pr(6))
[Pr(bta)0.5(H2bta)0.5]5H2O (7)
2.基于均苯四甲酸（偏苯三甲酸）与水合肼之间的原位酰胺化反应，合成了8个化合物。首次报道了均苯四甲酸与水合肼之间按1:1进行的原位酰胺化反应获得的4,5-苯二甲酸-1,2-酰肼（H4bbch）配体。
[Cu(H3bbch)(H2O)]2·2H2O (8)
[Fe3(Hbbch)2(H2O)2(H2O)2]·2H2O (9)
[Zn(H2bbh)(N2H4)1/2(H2O)]·2H2O (10)
[Cd(H2bch)2(2,2'-bpy)(H2O)2][Cd(H2bch)(2,2'-bpy)(H2O)2](H2bch)(11)
[Cd2(Hbch)2(phen)2]·H2O (12)
[Zn2(Hbch)2(phen)2]·H2O (13)
[Zn(Hbch)(2,2'-bpy)](14)
[Cd(bta)1/2(N2H4)(H2O)]·H2O (15)
3.利用4,4-联吡啶（bipy）作为有机配体，合成了6种基于Keggin型多酸的配合物；另外，也合成了1种含有1,10-邻菲罗啉（phen）以及1种含1,6-二（咪唑-1-氢）己烷（bbi）的基于Keggin型多酸的配合物。在合成中，pH和La(NO3)3对化合物16-21的最终结构起到关键的作用。
(SiMo12O40)(H2bipy)2·2H2O (16)
[Cu(Hbipy)4(HSiMo12O40)(SiMo12O40)](H2bipy)0.5·7H2O (17)
[Cu2(Hbipy)6(bipy)(SiMo12O40)3](Hbipy)2·6H2O (18)
[Cu2(bipy)2(SiMo12O40)](H2bipy)·2H2O (19)
[Cu2(bipy)4(H2O)4](SiMo12O40)·13H2O (20)
[Cu(bipy)]2(SiMo12O40)(H2bipy)·2H2O (21)
[SiMo12O40](H2bbi)2·2H2O (22)
[Cu2(phen)4(SiMo12O40)](23)(H4bta=benzene-1,2,4,5-tetracarboxylic acid; H4bbch=benzene-4,5-bicarboxylate-1,2-hydrazide; H4bbh=benzene-1,2,4,5-bihydrazide;H3bch=Benzene-4-carboxylate-1,2-hydrazide;2,2'-bpy=2,2'-bipyridine; phen=1,10-phenanthroline; bipy=4,4'-bipyridine; bbi=1,6-bis(imidazole-1-yl)hexane)
The main objective of this thesis is to design and investigate novelorganic-inorganic compounds, based on aromatic polycarboxylates orpolyoxometalates, which have been synthesized by hydrothermal synthesis method.The influences of reaction conditions and the mechanisms of synthesizing processwere investigated. The properties of these compounds were studied. Thesecompounds have been structurally characterized by single crystal X-ray diffractions,elemental analyses, IR and TG. The fluorescent activities of these compounds havealso been studied．
1. Seven three dimensional (3D) lanthanides compounds were hydrothermallysynthesized based on H4bta as an organic unit. Compounds5and6are composed oftwo dimensional (2D) metal-oxygen layers, and compound7contains onedimensional (1D) metal-oxygen chain. Three new coordination modes of H4bta arereported for the first time.
[Pr(bta)0.5(H2bta)0.5(H2O)](1)
[Eu2(bta)1.5(H2O)2](2)
[Ln2(bta)1.5(H2O)4]3H2O (Ln=La(3), Ce(4))
[Ln2(bta)1.5(H2O)2] H2O (Ln=Ce(5), Pr(6))
[Pr(bta)0.5(H2bta)0.5]5H2O (7)
2. Eight novel compounds were synthesized with in situ amidation hydrothermalreactions of aromatic polycarboxylates and hydrazine. H4bbch was firstly obtainedwith reaction of H4bta and hydrazine with a starting ratio of1:1.
[Cu(H3bbch)(H2O)]2·2H2O (8)
[Fe3(Hbbch)2(H2O)2(H2O)2]·2H2O (9)
[Zn(H2bbh)(N2H4)1/2(H2O)]·2H2O (10)
[Cd(H2bch)2(2,2'-bpy)(H2O)2][Cd(H2bch)(2,2'-bpy)(H2O)2](H2bch)(11)
[Cd2(Hbch)2(phen)2]·H2O (12)
[Zn2(Hbch)2(phen)2]·H2O (13)
[Zn(Hbch)(2,2'-bpy)](14)
[Cd(bta)1/2(N2H4)(H2O)]·H2O (15)
3. With utilization of4,4'-bipyridine (bipy) organic template, six Keggin-typepolyoxometalates based compounds were synthesized. In addition, two compoundsbased on Keggin-type polyoxometalates includes1,10-phenanthroline (phen) and 1,6-bis(imidazole-1-yl)hexane (bbi), respectively, have also been obtained. In thesynthesizing process, pH and La(NO3)3are the crucial issue for the final structures ofcompounds16-21.
(SiMo12O40)(H2bipy)2·2H2O (16)
[Cu(Hbipy)4(HSiMo12O40)(SiMo12O40)](H2bipy)0.5·7H2O (17)
[Cu2(Hbipy)6(bipy)(SiMo12O40)3](Hbipy)2·6H2O (18)
[Cu2(bipy)2(SiMo12O40)](H2bipy)·2H2O (19)
[Cu2(bipy)4(H2O)4](SiMo12O40)·13H2O (20)
[Cu(bipy)]2(SiMo12O40)(H2bipy)·2H2O (21)
[SiMo12O40](H2bbi)2·2H2O (22)
[Cu2(phen)4(SiMo12O40)](23)
(H4bta=benzene-1,2,4,5-tetracarboxylic acid; H4bbch=benzene-4,5-bicarboxylate-1,2-hydrazide; H4bbh=benzene-1,2,4,5-bihydrazide;H3bch=benzene-4-carboxylate-1,2-hydrazide;2,2'-bpy=2,2'-bipyridine; phen=1,10-phenanthroline; bipy=4,4'-bipyridine; bbi=1,6-bis(imidazole-1-yl)hexane)
1.以均苯四甲酸（H4bta）为有机配体，水热反应条件下合成了7个具有三维（3D）结构的稀土配位化合物。化合物5和6的结构中含有二维（2D）的金属-氧层，而化合物7的结构中含有一维（1D）的金属-氧链。首次报道了H4bta的三种新的配位模式。
[Pr(bta)0.5(H2bta)0.5(H2O)](1)
[Eu2(bta)1.5(H2O)2](2)
[Ln2(bta)1.5(H2O)4]3H2O (Ln=La(3), Ce(4))
[Ln2(bta)1.5(H2O)2] H2O (Ln=Ce(5), Pr(6))
[Pr(bta)0.5(H2bta)0.5]5H2O (7)
2.基于均苯四甲酸（偏苯三甲酸）与水合肼之间的原位酰胺化反应，合成了8个化合物。首次报道了均苯四甲酸与水合肼之间按1:1进行的原位酰胺化反应获得的4,5-苯二甲酸-1,2-酰肼（H4bbch）配体。
[Cu(H3bbch)(H2O)]2·2H2O (8)
[Fe3(Hbbch)2(H2O)2(H2O)2]·2H2O (9)
[Zn(H2bbh)(N2H4)1/2(H2O)]·2H2O (10)
[Cd(H2bch)2(2,2'-bpy)(H2O)2][Cd(H2bch)(2,2'-bpy)(H2O)2](H2bch)(11)
[Cd2(Hbch)2(phen)2]·H2O (12)
[Zn2(Hbch)2(phen)2]·H2O (13)
[Zn(Hbch)(2,2'-bpy)](14)
[Cd(bta)1/2(N2H4)(H2O)]·H2O (15)
3.利用4,4-联吡啶（bipy）作为有机配体，合成了6种基于Keggin型多酸的配合物；另外，也合成了1种含有1,10-邻菲罗啉（phen）以及1种含1,6-二（咪唑-1-氢）己烷（bbi）的基于Keggin型多酸的配合物。在合成中，pH和La(NO3)3对化合物16-21的最终结构起到关键的作用。
(SiMo12O40)(H2bipy)2·2H2O (16)
[Cu(Hbipy)4(HSiMo12O40)(SiMo12O40)](H2bipy)0.5·7H2O (17)
[Cu2(Hbipy)6(bipy)(SiMo12O40)3](Hbipy)2·6H2O (18)
[Cu2(bipy)2(SiMo12O40)](H2bipy)·2H2O (19)
[Cu2(bipy)4(H2O)4](SiMo12O40)·13H2O (20)
[Cu(bipy)]2(SiMo12O40)(H2bipy)·2H2O (21)
[SiMo12O40](H2bbi)2·2H2O (22)
[Cu2(phen)4(SiMo12O40)](23)(H4bta=benzene-1,2,4,5-tetracarboxylic acid; H4bbch=benzene-4,5-bicarboxylate-1,2-hydrazide; H4bbh=benzene-1,2,4,5-bihydrazide;H3bch=Benzene-4-carboxylate-1,2-hydrazide;2,2'-bpy=2,2'-bipyridine; phen=1,10-phenanthroline; bipy=4,4'-bipyridine; bbi=1,6-bis(imidazole-1-yl)hexane)
The main objective of this thesis is to design and investigate novelorganic-inorganic compounds, based on aromatic polycarboxylates orpolyoxometalates, which have been synthesized by hydrothermal synthesis method.The influences of reaction conditions and the mechanisms of synthesizing processwere investigated. The properties of these compounds were studied. Thesecompounds have been structurally characterized by single crystal X-ray diffractions,elemental analyses, IR and TG. The fluorescent activities of these compounds havealso been studied．
1. Seven three dimensional (3D) lanthanides compounds were hydrothermallysynthesized based on H4bta as an organic unit. Compounds5and6are composed oftwo dimensional (2D) metal-oxygen layers, and compound7contains onedimensional (1D) metal-oxygen chain. Three new coordination modes of H4bta arereported for the first time.
[Pr(bta)0.5(H2bta)0.5(H2O)](1)
[Eu2(bta)1.5(H2O)2](2)
[Ln2(bta)1.5(H2O)4]3H2O (Ln=La(3), Ce(4))
[Ln2(bta)1.5(H2O)2] H2O (Ln=Ce(5), Pr(6))
[Pr(bta)0.5(H2bta)0.5]5H2O (7)
2. Eight novel compounds were synthesized with in situ amidation hydrothermalreactions of aromatic polycarboxylates and hydrazine. H4bbch was firstly obtainedwith reaction of H4bta and hydrazine with a starting ratio of1:1.
[Cu(H3bbch)(H2O)]2·2H2O (8)
[Fe3(Hbbch)2(H2O)2(H2O)2]·2H2O (9)
[Zn(H2bbh)(N2H4)1/2(H2O)]·2H2O (10)
[Cd(H2bch)2(2,2'-bpy)(H2O)2][Cd(H2bch)(2,2'-bpy)(H2O)2](H2bch)(11)
[Cd2(Hbch)2(phen)2]·H2O (12)
[Zn2(Hbch)2(phen)2]·H2O (13)
[Zn(Hbch)(2,2'-bpy)](14)
[Cd(bta)1/2(N2H4)(H2O)]·H2O (15)
3. With utilization of4,4'-bipyridine (bipy) organic template, six Keggin-typepolyoxometalates based compounds were synthesized. In addition, two compoundsbased on Keggin-type polyoxometalates includes1,10-phenanthroline (phen) and 1,6-bis(imidazole-1-yl)hexane (bbi), respectively, have also been obtained. In thesynthesizing process, pH and La(NO3)3are the crucial issue for the final structures ofcompounds16-21.
(SiMo12O40)(H2bipy)2·2H2O (16)
[Cu(Hbipy)4(HSiMo12O40)(SiMo12O40)](H2bipy)0.5·7H2O (17)
[Cu2(Hbipy)6(bipy)(SiMo12O40)3](Hbipy)2·6H2O (18)
[Cu2(bipy)2(SiMo12O40)](H2bipy)·2H2O (19)
[Cu2(bipy)4(H2O)4](SiMo12O40)·13H2O (20)
[Cu(bipy)]2(SiMo12O40)(H2bipy)·2H2O (21)
[SiMo12O40](H2bbi)2·2H2O (22)
[Cu2(phen)4(SiMo12O40)](23)
(H4bta=benzene-1,2,4,5-tetracarboxylic acid; H4bbch=benzene-4,5-bicarboxylate-1,2-hydrazide; H4bbh=benzene-1,2,4,5-bihydrazide;H3bch=benzene-4-carboxylate-1,2-hydrazide;2,2'-bpy=2,2'-bipyridine; phen=1,10-phenanthroline; bipy=4,4'-bipyridine; bbi=1,6-bis(imidazole-1-yl)hexane)
引文
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