氮杂环及含羧基类配体官能化多钼酸盐的合成及性质研究
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摘要
本论文旨在利用含氮杂环或羧基类配体与原位生成的多钼酸盐阴离子反应,构筑新型具有一定功能特性的多钼酸盐官能化衍生物。研究这类化合物的合成条件及反应规律,探讨反应过程中的pH值、抗衡阳离子、溶剂、配位原子电荷密度等因素对化合物结构形成的影响。在分子设计思想的指导下,实验中所得到的化合物不仅实现了氮杂环或羧基类配体通过不同强度的共价键与多钼酸盐阴离子的连接,而且实现了多钼酸盐衍生物的结构从零维到三维的变化。
在实验中我们选用吡啶类衍生物、咪唑、多元羧酸、二氧化碳、含羧基的铜配合物等作为修饰配体,不同的多钼酸盐为无机组分,在常规条件下通过调节反应原料的种类和反应条件合成了十六种未见文献报道的多钼酸盐衍生物。通过元素分析、红外光谱、X-射线光电子能谱、电化学分析和单晶X-射线衍射分析等手段对这些化合物的晶体结构和性质进行了表征。
1.利用有机配体烟酰胺或异烟酸在水溶液中与原位生成的八钼酸盐反应合成并表征了四个有机配体修饰的多钼酸盐衍生物:
化合物1–3实现了烟酰胺配体与γ?构型八钼酸盐的官能化反应。三个化合物中的阴离子骨架结构相似。但是由于钠离子的堆积不同,化合物2与3中钠离子连接的阴离子骨架分别呈现一维链和二维层状结构。化合物4中的吡啶氮原子没有与阴离子配位因此只形成了氢键连接的超分子化合物。
2.利用有机配体咪唑,在水溶液或混合溶剂中与钼酸盐及过渡金属离子反应,合成并表征了四个咪唑诱导的多钼酸盐衍生物:
化合物5中无机骨架单元为两种咪唑官能化的γ-型八钼酸盐多阴离子,这些多阴离子利用钾离子与配合物阳离子的连接形成了具有一维孔道的三维化合物。6与7虽然是在相同的条件下合成产生,但所得结构却完全不同:化合物6中的阴离子骨架为结构新颖的首例Co2+离子作为中心杂原子的Keggin型杂多钼酸盐;而化合物7则呈现[Co(H2O)5]2+水合离子与七钼酸盐通过共用氧原子相连形成的简单阴离子结构。化合物8的合成条件与6和7虽然相近仅是在反应体系中引入了N,N’-二甲基酰胺溶剂,但晶体结构却与6和7完全不同。化合物8中与咪唑配位的[Co(imi)2(H2O)2]2+配合物阳离子将七钼酸盐连接成为一维链式结构。
3.利用含羧基的有机配体在水溶液中与钼酸盐反应,合成并表征了四个羧基官能化的多钼酸盐衍生物:
化合物9与10分别实现了脂肪族与芳香族羧酸配体官能化γ-型八钼酸盐多阴离子的反应。化合物11与12则实现了多羧基配体与新型十钼酸盐的官能化反应,而且有机配体与十钼酸盐之间通过三个配位键使有机与无机两种阴离子之间的结合力增强。11与12还呈现出少见报道的内消旋链结构。化合物11与聚乙烯醇组成的复合膜还具有光致变色性质。
4.在二氧化碳的参与下,利用常规水溶液合成方法制备出两种以共价键结合的链状二氧化碳官能化的杂多钼酸盐:
在化合物13与14中,CO2分子通过两个氧原子与相邻的[PMo11CoO39(H2O)]5-或[SiMo11CoO39(H2O)]6-多阴离子之间以共价键连接形成了一维链状结构。首次实现了多阴离子与CO2分子的官能化反应,即实现了CO2分子的化学共价键固载。
5.在水/N, N’-二甲基甲酰胺混合体系中,用预先制备的铜配合物与原位生成的多钼酸盐反应,分别制备出链状或层状的铜配合物修饰的八钼酸盐化合物:
化合物15利用两步合成的方法,证明了多钼酸盐阴离子的端氧可以取代配合物中弱的配体,并发现多阴离子可以通过改变配合物前驱体的构型来实现磁学性质的调变。化合物16进一步实现了配合物中有机基团和中心离子同时与多钼酸盐阴离子的配位并得到层状二维结构。化合物16的磁学性质研究也表明多阴离子的取代对配合物的磁性可以产生较大的影响。
In this thesis, N-heterocycle or carboxylic ligands were used to react with in-situ generated polymolybdate anion to construct functionalized polymolybdate derivative with certain functions. The influence of the reaction conditions for the final products was investigated such as pH, counterion, solvent, and charge density of coordination atom. By way of molecular design, N-heterocycle or carboxylic ligands were realized to coordinate to the polymolybdate anions by different covalent bonds. The structures of these new functionalized polymolybdate compounds also vary from 0D to 3D.
Under conventional conditions, we select pyridine derivative, imidazole, multi-carboxylic acids, carbon dioxide, and carboxyl containing copper complex as organic ligands to react with polymolybdate inorganic component and new sixteen polymolybdate compounds were successful synthesized. These new complexes were characterized by elemental analysis, IR and XPS spectra, TGA, electrochemical and XRD single crystal analysis.
1. In aqueous phase, four polymolybdate derivatives were synthesized by using nicotinic amide or nicotinic acid as organic ligands:
Compounds 1?3 realized the functionalization of nicotinamide withγ?type octamolybdate. Due to the different arrangement of Na+ ions, compounds 2 and 3 display 1D chain and 2D layered structures, respectively. While compound 4 only shows H-bond linked supramolecular framework, because the N atom in nicotinic acid does not coordinate to the polyanion.
2. In aqueous or mixed phase, imidazole and transition metal ion react with molybdate forming four imidazole-containing polymolybdate derivatives:
Compound 5 contains the imidazole functionlizedγ?type octamolybdate polyanion. These polyanions together with K+ and copper complex cations to form 3D framework with 1D channel. Under the same conditions, compounds 6 and 7 present different structures: compound 6 is the first example of Keggin-type heteropolymolybdate with Co2+ ion as central heteroatom; while compound 7 only contains a heptmolybdate anion coordinated by a [Co(H2O)5]2+ cation. In mixed solvent, compound 8 represent a 1D chain structure that the heptmolybdate anions are linked by [Co(imi)2(H2O)2]2+ cations.
3. In aqueous phase, the carboxylic ligands were used to react with molybdate and four carboxyl functionalized polymolybdate formed:
Compounds 9 and 10 realize the functionalization of carboxyl withγ?type octamolybdate polyanion. Compounds 11 and 12 realize the functionalization of carboxyl with decamolybdate polyanion, where the multi-carboxylic acids coordinate to the decamolybdate anions by three covalent bonds and present interesting meso-helical chain structures. In addition, the film containing 11and polyvinyl shows photochromic properties.
4. In aqueous phase, two heteropolymolybdate were functionalized by carbon dioxide ligands:
In compounds 13 and 14, CO2 ligand coordinates to the [PMo11CoO39(H2O)]5- or [SiMo11CoO39(H2O)]6- anions by its oxygen atoms, showing 1D chain-like structures. It is the first time to realize the coordination of CO2 by polyoxoanions.
5. In water/DMF mixed solvent, the as-synthesized copper complex was used as ligand to react with polymolybdate and chain-like or layered octamolybdate compounds were isolated:
Using two-step synthetic method, compound 15 confirm that the terminal oxygen atom can substitute the weak ligand in the copper complex. It was also found that the magnetic properties can be modulated by the conformation change of the as-synthesized copper complex (CuL1). Compound 16 further realized the coordination of carboxyl and copper ion with polymolybdate anions simultaneously and present 2D layered structure. Magnetism of compound 16 also indicates that the substituted polyanion can affect the magnetic properties of as-synthesized copper complex (CuL2).
在实验中我们选用吡啶类衍生物、咪唑、多元羧酸、二氧化碳、含羧基的铜配合物等作为修饰配体,不同的多钼酸盐为无机组分,在常规条件下通过调节反应原料的种类和反应条件合成了十六种未见文献报道的多钼酸盐衍生物。通过元素分析、红外光谱、X-射线光电子能谱、电化学分析和单晶X-射线衍射分析等手段对这些化合物的晶体结构和性质进行了表征。
1.利用有机配体烟酰胺或异烟酸在水溶液中与原位生成的八钼酸盐反应合成并表征了四个有机配体修饰的多钼酸盐衍生物:
化合物1–3实现了烟酰胺配体与γ?构型八钼酸盐的官能化反应。三个化合物中的阴离子骨架结构相似。但是由于钠离子的堆积不同,化合物2与3中钠离子连接的阴离子骨架分别呈现一维链和二维层状结构。化合物4中的吡啶氮原子没有与阴离子配位因此只形成了氢键连接的超分子化合物。
2.利用有机配体咪唑,在水溶液或混合溶剂中与钼酸盐及过渡金属离子反应,合成并表征了四个咪唑诱导的多钼酸盐衍生物:
化合物5中无机骨架单元为两种咪唑官能化的γ-型八钼酸盐多阴离子,这些多阴离子利用钾离子与配合物阳离子的连接形成了具有一维孔道的三维化合物。6与7虽然是在相同的条件下合成产生,但所得结构却完全不同:化合物6中的阴离子骨架为结构新颖的首例Co2+离子作为中心杂原子的Keggin型杂多钼酸盐;而化合物7则呈现[Co(H2O)5]2+水合离子与七钼酸盐通过共用氧原子相连形成的简单阴离子结构。化合物8的合成条件与6和7虽然相近仅是在反应体系中引入了N,N’-二甲基酰胺溶剂,但晶体结构却与6和7完全不同。化合物8中与咪唑配位的[Co(imi)2(H2O)2]2+配合物阳离子将七钼酸盐连接成为一维链式结构。
3.利用含羧基的有机配体在水溶液中与钼酸盐反应,合成并表征了四个羧基官能化的多钼酸盐衍生物:
化合物9与10分别实现了脂肪族与芳香族羧酸配体官能化γ-型八钼酸盐多阴离子的反应。化合物11与12则实现了多羧基配体与新型十钼酸盐的官能化反应,而且有机配体与十钼酸盐之间通过三个配位键使有机与无机两种阴离子之间的结合力增强。11与12还呈现出少见报道的内消旋链结构。化合物11与聚乙烯醇组成的复合膜还具有光致变色性质。
4.在二氧化碳的参与下,利用常规水溶液合成方法制备出两种以共价键结合的链状二氧化碳官能化的杂多钼酸盐:
在化合物13与14中,CO2分子通过两个氧原子与相邻的[PMo11CoO39(H2O)]5-或[SiMo11CoO39(H2O)]6-多阴离子之间以共价键连接形成了一维链状结构。首次实现了多阴离子与CO2分子的官能化反应,即实现了CO2分子的化学共价键固载。
5.在水/N, N’-二甲基甲酰胺混合体系中,用预先制备的铜配合物与原位生成的多钼酸盐反应,分别制备出链状或层状的铜配合物修饰的八钼酸盐化合物:
化合物15利用两步合成的方法,证明了多钼酸盐阴离子的端氧可以取代配合物中弱的配体,并发现多阴离子可以通过改变配合物前驱体的构型来实现磁学性质的调变。化合物16进一步实现了配合物中有机基团和中心离子同时与多钼酸盐阴离子的配位并得到层状二维结构。化合物16的磁学性质研究也表明多阴离子的取代对配合物的磁性可以产生较大的影响。
In this thesis, N-heterocycle or carboxylic ligands were used to react with in-situ generated polymolybdate anion to construct functionalized polymolybdate derivative with certain functions. The influence of the reaction conditions for the final products was investigated such as pH, counterion, solvent, and charge density of coordination atom. By way of molecular design, N-heterocycle or carboxylic ligands were realized to coordinate to the polymolybdate anions by different covalent bonds. The structures of these new functionalized polymolybdate compounds also vary from 0D to 3D.
Under conventional conditions, we select pyridine derivative, imidazole, multi-carboxylic acids, carbon dioxide, and carboxyl containing copper complex as organic ligands to react with polymolybdate inorganic component and new sixteen polymolybdate compounds were successful synthesized. These new complexes were characterized by elemental analysis, IR and XPS spectra, TGA, electrochemical and XRD single crystal analysis.
1. In aqueous phase, four polymolybdate derivatives were synthesized by using nicotinic amide or nicotinic acid as organic ligands:
Compounds 1?3 realized the functionalization of nicotinamide withγ?type octamolybdate. Due to the different arrangement of Na+ ions, compounds 2 and 3 display 1D chain and 2D layered structures, respectively. While compound 4 only shows H-bond linked supramolecular framework, because the N atom in nicotinic acid does not coordinate to the polyanion.
2. In aqueous or mixed phase, imidazole and transition metal ion react with molybdate forming four imidazole-containing polymolybdate derivatives:
Compound 5 contains the imidazole functionlizedγ?type octamolybdate polyanion. These polyanions together with K+ and copper complex cations to form 3D framework with 1D channel. Under the same conditions, compounds 6 and 7 present different structures: compound 6 is the first example of Keggin-type heteropolymolybdate with Co2+ ion as central heteroatom; while compound 7 only contains a heptmolybdate anion coordinated by a [Co(H2O)5]2+ cation. In mixed solvent, compound 8 represent a 1D chain structure that the heptmolybdate anions are linked by [Co(imi)2(H2O)2]2+ cations.
3. In aqueous phase, the carboxylic ligands were used to react with molybdate and four carboxyl functionalized polymolybdate formed:
Compounds 9 and 10 realize the functionalization of carboxyl withγ?type octamolybdate polyanion. Compounds 11 and 12 realize the functionalization of carboxyl with decamolybdate polyanion, where the multi-carboxylic acids coordinate to the decamolybdate anions by three covalent bonds and present interesting meso-helical chain structures. In addition, the film containing 11and polyvinyl shows photochromic properties.
4. In aqueous phase, two heteropolymolybdate were functionalized by carbon dioxide ligands:
In compounds 13 and 14, CO2 ligand coordinates to the [PMo11CoO39(H2O)]5- or [SiMo11CoO39(H2O)]6- anions by its oxygen atoms, showing 1D chain-like structures. It is the first time to realize the coordination of CO2 by polyoxoanions.
5. In water/DMF mixed solvent, the as-synthesized copper complex was used as ligand to react with polymolybdate and chain-like or layered octamolybdate compounds were isolated:
Using two-step synthetic method, compound 15 confirm that the terminal oxygen atom can substitute the weak ligand in the copper complex. It was also found that the magnetic properties can be modulated by the conformation change of the as-synthesized copper complex (CuL1). Compound 16 further realized the coordination of carboxyl and copper ion with polymolybdate anions simultaneously and present 2D layered structure. Magnetism of compound 16 also indicates that the substituted polyanion can affect the magnetic properties of as-synthesized copper complex (CuL2).
引文
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