含氮氧配体金属配合物的合成、晶体结构和性质研究
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摘要
金属-有机配位聚合物是由金属中心离子与有机配体通过配位键的作用以及其它化学作用形成的,其多样化的结构导致了许多特殊的性能。
本文通过水热法和液相扩散法合成了一系列具有新型结构的金属-有机配位聚合物,并通过红外光谱、元素分析、X-射线单晶衍射和热重分析等方法,对其结构和热稳定性进行了表征。主要内容如下:
1.利用单一配体2,2'-联吡啶合成了一种简单的金属-有机配位聚合物Ⅰ:[Cu_4(bpy)_4(OH)_4]Cl_4·6H_2O。在此基础上,添加芳香二羧酸配体又合成出了两种配合Ⅱ:[Cu_2(C_(10)H_8N_2)_2(C_8H_4O_5)_2(H_2O)_2]和Ⅲ:{[Cu_2(bpy)(tpa)_2(bpy)]·H_2O}_n。其中Ⅰ是四核配合物,含有大量的分子间氢键(O-H…Cl和O-H…O),这些氢键沿着b轴方向形成交替连接的六元环和八元环。配合物Ⅱ的三维结构比较新颖,具有双核中心结构。在合成Ⅱ的过程中,间苯二甲酸在水热反应中被原位羟基化,证明了水热合成法容易产生结构新颖的配合物的优点。配合物Ⅲ的三维结构是由沿不同方向的两组平行一维“之”字链之间通过氢键和芳香(杂)环之间的π-π堆积作用而产生的。
2.选用烟酸做配体合成了两种配合物Ⅳ:[Cu(NcA)_2]_∞和Ⅴ:[Cu(NcA)_2(H_2O)_4]。由于烟酸配体两种不同的配位原子N和O以及它们与Cu(Ⅱ)键合能力的不同,化合物Ⅳ和Ⅴ具有完全不同的结构特点:在化合物Ⅳ中,烟酸配体的N和O均与Cu(Ⅱ)配位,Ⅳ具有纯粹依靠共价键和配位键形成的无限三维网络结构;在化合物Ⅴ中仅有N与Cu(Ⅱ)配位,其结构在分子间O-H...O氢键和芳香杂环之间的π-π作用下扩展成无限二维面结构。
3.在合成出配合物V后,我们加入与O配位能力较强的稀土金属盐,合成出了一种3d-4f异核化合物Ⅵ:[LaCu_3(C_8H_3O_5)_3(H_2O)_3]_n。和一种稀土金属配合物Ⅶ[Nd_2(C_8H_6O_4)_4(H_2O)]·H_2O。合成方法的不同再加上羧酸根配体的丰富的配位模式使得Ⅵ和Ⅶ的结构迥异。在水热合成化合物Ⅵ的过程中,间苯二甲酸配体同样发生了原位羟基化反应。化合物Ⅶ是采用液相扩散法合成的,因此间苯二甲酸配体直接与稀土金属离子配位。由于稀土离子的配位数比较高,因此在配合物中都含有大量的配位水分子,进而存在大量的分子内和分子间O-H...O氢键作用力,在进一步稳定化合物结构的同时将其扩展成无限三维网络结构。
Metalorganic coordination polymers are formed by the coordination bonds between organic ligands and metal ions. Diversified structures of the coordination polymers resulted in unusual properties of the novel materials.
In this thesis, seven metal-organic coordination polymers with novel structures were hydrothermally synthesized. Structures and thermal stabilization of these coordination polymers were characterized by infrared spectra, elemental analysis, X-ray single crystal diffraction and thermal gravity methods. The main contents are as follows:
1. 2,2'-bipyridine was used to synthesize one simple metal-organic coordination polymerⅠ:[Cu_4(bpy)_4(OH)_4]Cl_4·6H_2O. Benzendicaiboxylic acids were then added to synthesize coordination polymersⅡ:[Cu_2(C_(10)H_8N_2)_2(C_8H_4O_5)_2(H_2O)_2] andⅢ:{[Cu_2(bpy)(tpa)_2(bpy)]·H_2O}_n. Among them,Ⅰis tetra-nuclears structure which contains abundant inter-molecular hydrogen bonds O-H…Cl and O-H…O. These hydrogen bonds alternatively formed six-member and eight-member rings along b direction.Ⅱhas a novel three-dimensional network with a kind of binuclear-centered structure. In the process of synthesizingⅡ, isophthalic acid underwent in-situ oxidative hydroxylation before coordinating with Cu (Ⅱ) ion, proving that coordination compounds with novel structures are easily achieved by hydrothermal synthesis. The three-dimensional network ofⅢis constructed by inter-molecular hydrogen bonds andπ-πstacking interactions existing between two parallel "zigzag" chains in two different directions.
2. Nicotinic acid was chosen as the ligand which contains N and O as the coordination atoms. Coordination polymersⅣ:[Cu(NcA)_2]_∞andⅤ:[Cu(NcA)_2(H_2O)_4] were synthesized. Due to the different bond abilities of N and O with Cu(Ⅱ), the structures ofⅣandⅤare different from each other. InⅣ, both N and O were bonded with Cu(Ⅱ) while only N did so inⅤ. Besides, the structure ofⅣis three-dimensional which was constructed by covalent bonds and coordinated bonds whileⅤhas a two-dimensional face structure extended by O-H…O hydrogen bonds andπ-πstacking interactions.
3. On the basis of the synthesis ofⅤ, rare earth metal ions were added which have stronger bond abilities with O compared with N. One heteronuclear coordination polymerⅥ[LaCu_3(C_8H_3O_5)_3(H_2O)_3]_n and one rare earth metal-organic coordination polymerⅦ[Nd_2(C_8H_6O_4)_4(H_2O)]·H_2O were synthesized. InⅥ, isophthalic acid was also in-situ oxidative hydroxylated like that inⅡ. While inⅦwhich was produced by liquid diffusion isophthalic acid was directly coordinated with Nd(Ⅲ). Because the coordination number of rare earth metal ions is usually high, so a plenty of coordinated water molecules existed inⅥandⅦ, which further formed abundant hydrogen bonds. These hydrogen bonds helped to stabilize the structures ofⅥandⅦwhile at the same time extended them into three-dimensional networks.
本文通过水热法和液相扩散法合成了一系列具有新型结构的金属-有机配位聚合物,并通过红外光谱、元素分析、X-射线单晶衍射和热重分析等方法,对其结构和热稳定性进行了表征。主要内容如下:
1.利用单一配体2,2'-联吡啶合成了一种简单的金属-有机配位聚合物Ⅰ:[Cu_4(bpy)_4(OH)_4]Cl_4·6H_2O。在此基础上,添加芳香二羧酸配体又合成出了两种配合Ⅱ:[Cu_2(C_(10)H_8N_2)_2(C_8H_4O_5)_2(H_2O)_2]和Ⅲ:{[Cu_2(bpy)(tpa)_2(bpy)]·H_2O}_n。其中Ⅰ是四核配合物,含有大量的分子间氢键(O-H…Cl和O-H…O),这些氢键沿着b轴方向形成交替连接的六元环和八元环。配合物Ⅱ的三维结构比较新颖,具有双核中心结构。在合成Ⅱ的过程中,间苯二甲酸在水热反应中被原位羟基化,证明了水热合成法容易产生结构新颖的配合物的优点。配合物Ⅲ的三维结构是由沿不同方向的两组平行一维“之”字链之间通过氢键和芳香(杂)环之间的π-π堆积作用而产生的。
2.选用烟酸做配体合成了两种配合物Ⅳ:[Cu(NcA)_2]_∞和Ⅴ:[Cu(NcA)_2(H_2O)_4]。由于烟酸配体两种不同的配位原子N和O以及它们与Cu(Ⅱ)键合能力的不同,化合物Ⅳ和Ⅴ具有完全不同的结构特点:在化合物Ⅳ中,烟酸配体的N和O均与Cu(Ⅱ)配位,Ⅳ具有纯粹依靠共价键和配位键形成的无限三维网络结构;在化合物Ⅴ中仅有N与Cu(Ⅱ)配位,其结构在分子间O-H...O氢键和芳香杂环之间的π-π作用下扩展成无限二维面结构。
3.在合成出配合物V后,我们加入与O配位能力较强的稀土金属盐,合成出了一种3d-4f异核化合物Ⅵ:[LaCu_3(C_8H_3O_5)_3(H_2O)_3]_n。和一种稀土金属配合物Ⅶ[Nd_2(C_8H_6O_4)_4(H_2O)]·H_2O。合成方法的不同再加上羧酸根配体的丰富的配位模式使得Ⅵ和Ⅶ的结构迥异。在水热合成化合物Ⅵ的过程中,间苯二甲酸配体同样发生了原位羟基化反应。化合物Ⅶ是采用液相扩散法合成的,因此间苯二甲酸配体直接与稀土金属离子配位。由于稀土离子的配位数比较高,因此在配合物中都含有大量的配位水分子,进而存在大量的分子内和分子间O-H...O氢键作用力,在进一步稳定化合物结构的同时将其扩展成无限三维网络结构。
Metalorganic coordination polymers are formed by the coordination bonds between organic ligands and metal ions. Diversified structures of the coordination polymers resulted in unusual properties of the novel materials.
In this thesis, seven metal-organic coordination polymers with novel structures were hydrothermally synthesized. Structures and thermal stabilization of these coordination polymers were characterized by infrared spectra, elemental analysis, X-ray single crystal diffraction and thermal gravity methods. The main contents are as follows:
1. 2,2'-bipyridine was used to synthesize one simple metal-organic coordination polymerⅠ:[Cu_4(bpy)_4(OH)_4]Cl_4·6H_2O. Benzendicaiboxylic acids were then added to synthesize coordination polymersⅡ:[Cu_2(C_(10)H_8N_2)_2(C_8H_4O_5)_2(H_2O)_2] andⅢ:{[Cu_2(bpy)(tpa)_2(bpy)]·H_2O}_n. Among them,Ⅰis tetra-nuclears structure which contains abundant inter-molecular hydrogen bonds O-H…Cl and O-H…O. These hydrogen bonds alternatively formed six-member and eight-member rings along b direction.Ⅱhas a novel three-dimensional network with a kind of binuclear-centered structure. In the process of synthesizingⅡ, isophthalic acid underwent in-situ oxidative hydroxylation before coordinating with Cu (Ⅱ) ion, proving that coordination compounds with novel structures are easily achieved by hydrothermal synthesis. The three-dimensional network ofⅢis constructed by inter-molecular hydrogen bonds andπ-πstacking interactions existing between two parallel "zigzag" chains in two different directions.
2. Nicotinic acid was chosen as the ligand which contains N and O as the coordination atoms. Coordination polymersⅣ:[Cu(NcA)_2]_∞andⅤ:[Cu(NcA)_2(H_2O)_4] were synthesized. Due to the different bond abilities of N and O with Cu(Ⅱ), the structures ofⅣandⅤare different from each other. InⅣ, both N and O were bonded with Cu(Ⅱ) while only N did so inⅤ. Besides, the structure ofⅣis three-dimensional which was constructed by covalent bonds and coordinated bonds whileⅤhas a two-dimensional face structure extended by O-H…O hydrogen bonds andπ-πstacking interactions.
3. On the basis of the synthesis ofⅤ, rare earth metal ions were added which have stronger bond abilities with O compared with N. One heteronuclear coordination polymerⅥ[LaCu_3(C_8H_3O_5)_3(H_2O)_3]_n and one rare earth metal-organic coordination polymerⅦ[Nd_2(C_8H_6O_4)_4(H_2O)]·H_2O were synthesized. InⅥ, isophthalic acid was also in-situ oxidative hydroxylated like that inⅡ. While inⅦwhich was produced by liquid diffusion isophthalic acid was directly coordinated with Nd(Ⅲ). Because the coordination number of rare earth metal ions is usually high, so a plenty of coordinated water molecules existed inⅥandⅦ, which further formed abundant hydrogen bonds. These hydrogen bonds helped to stabilize the structures ofⅥandⅦwhile at the same time extended them into three-dimensional networks.
引文
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