金属有机杂化材料的结构设计与性能表征
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摘要
材料的宏观性能与其微观结构有着紧密的关系。本论文以探讨金属有机杂化材料的结构设计与性能为目的,开展了系列化合物合成与表征方面的研究工作。金属有机杂化材料的制备过程与其它多孔框架材料类似,模板剂的种类和构型对材料最终的结构主题有着重要的影响作用。在本文的工作中,我们引入阴离子Cl-作为模板剂,于1,2,4-苯三甲酸与2,5-吡啶二羧酸的混配体系中合成出了一例新型的二维金属有机混杂材料[Zn2(BTC)(PDC)?3H2O]Cl,通过元素分析、热重(TGA)、粉末X射线衍射(XPRD)、红外以及荧光光谱分析等多项相关表征,对Zn2+与1,2,4-苯三甲酸和2,5-吡啶二羧酸混杂配位合成中的各种影响因素进行了研究与探讨。实验显示氯离子在模板诱导合成混杂配体框架的过程起到了重要的作用。与此相比较,如用F-、Br-、I-、PO43-离子代替Cl-为模板离子,只能得到含2,5-吡啶二羧酸的单配位框架结构。结果表明氯离子与框架结构之间存在着独特的主体-客体识别作用。
金属有机杂化材料的结构堆积方式与荧光特性紧密相联。通过对自由TPT(2,4,6-三(4-吡啶基)-1,3,5-三嗪)配体和其与Zn配位合成化合物Zn(TPT)2(H2O)4(OH)2的结构表征,发现配位后TPT的π-π堆积模式由错位堆积转变为完美的面对面堆积。结构的变化同时也影响到了物质的固体荧光性能。在360nm的波长激发下,自由状态的TPT在450nm显示出了强烈的荧光发射峰,但是配位后的物质在同样位置的发射强度却大为减弱,这主要是由于配位后层间距的增加而造成的。
金属与有机配体混杂间存在着有趣的能量转移现象,可望开拓成为新类型的光色材料。利用TPT和Zn分别与1,2,4-苯三甲酸以及1,3,5-苯三甲酸相配位,制备出两例新的混杂框架材料Zn(TPT)(BTC)H2O和Zn3(TPT)(BTC)2(H2O)6。其中化合物Zn(TPT)(BTC)H2O表现出了明显的光致变色性能,而化合物Zn3(TPT)(BTC)2(H2O)6的变色性能不明显。这也与两种化合物的结构密切相关。在化合物Zn(TPT)(BTC)H2O中,TPT的三个吡啶氮并未全部配位,而是留下了一个悬空的配位点,导致分子内部存在着较强的极化度。而在化合物Zn3(TPT)(BTC)2(H2O)6中,TPT的三个位点全部配位,电荷分布均匀,没有极化现象。分子极化导致了电子云的排布的差异使得光致变色性能发生改变。对于化合物Zn(TPT)(BTC)H2O中未配位的吡啶基,进行相关化学修饰方面的探索,考察相关的性能变化。
The characters of the materials are related to the constructions. In this paper, with the purpose of designing and synthesis new metal organic frameworks, we did lots of works on synthesis and characterizing. As most of synthetic reactions, template has been revealed as important factor that goven the structure, so does the MOFs. In this paper, a new two-dimensional metal organic framework is synthesized and characterized. The encapsulated chloride anions organize a collection of building units into a novel mixed-ligand metal organic supramolecular assembly, indicating specific host-guest recognition. By constrast, the addition of F-、Br-、I-、PO4- anions only give out the coordination complexes with single ligand. Reactions of the Zn2+ ion with 1,2,4-benzenetricarboxylic acid have been investigated with emphasis on the facors that govern reaction results. And the sample is characterized by the elemental analysis, TGA, XPRD, IR, and luminescent data.
In addition, the relations between the luminescence characters and constructions are also investigated.π-πstacking in the 2,4,6-tris(4-pyridyl)-1,3,5-triazine aromatic nitrogen-containing ligand and its metal-ligand complex Zn(TPT)2(H2O)4(OH)2 1 have been investigated by single-crystal X-ray diffraction analyses. The stacking mode of the ligand change from the offset conformation to a face-to-face perfect alignment with the coordination to the zinc centers. The structure features have correlated with their solid-state luminescence properties. With excited at 360nm, free TPT ligand gives a strong fluorescent emission at 455nm and the ligand-centered emission of the metal-ligand complex occurs at the same wavelength with lower emission intensity. The distance between the aromatic rings respond to the difference of the luminescence characters.
Otherwise, the MOFs could become photochromic materials based on the interesting energy transition among the moleculars.Two new mixed-ligand metal organic frameworks Zn(TPT)(BTC)H2O and Zn3(TPT)(BTC)2(H2O)6 are also synthesized and characterized. Compared with the Zn3(TPT)(BTC)2(H2O)6, Zn(TPT)(BTC)H2O displayed strong photochromic phenomenon. As in Zn(TPT)(BTC)H2O, there is a un-coordinated atom N, and the charge distribution in TPT is imbalance. Contrarily, the charge distribution in Zn3(TPT)(BTC)2(H2O)6 is symmetrical, and the difference respond to the diversity of the photochromic characters. Post modification with pyridine in Zn(TPT)(BTC)H2O also has been investigated.
金属有机杂化材料的结构堆积方式与荧光特性紧密相联。通过对自由TPT(2,4,6-三(4-吡啶基)-1,3,5-三嗪)配体和其与Zn配位合成化合物Zn(TPT)2(H2O)4(OH)2的结构表征,发现配位后TPT的π-π堆积模式由错位堆积转变为完美的面对面堆积。结构的变化同时也影响到了物质的固体荧光性能。在360nm的波长激发下,自由状态的TPT在450nm显示出了强烈的荧光发射峰,但是配位后的物质在同样位置的发射强度却大为减弱,这主要是由于配位后层间距的增加而造成的。
金属与有机配体混杂间存在着有趣的能量转移现象,可望开拓成为新类型的光色材料。利用TPT和Zn分别与1,2,4-苯三甲酸以及1,3,5-苯三甲酸相配位,制备出两例新的混杂框架材料Zn(TPT)(BTC)H2O和Zn3(TPT)(BTC)2(H2O)6。其中化合物Zn(TPT)(BTC)H2O表现出了明显的光致变色性能,而化合物Zn3(TPT)(BTC)2(H2O)6的变色性能不明显。这也与两种化合物的结构密切相关。在化合物Zn(TPT)(BTC)H2O中,TPT的三个吡啶氮并未全部配位,而是留下了一个悬空的配位点,导致分子内部存在着较强的极化度。而在化合物Zn3(TPT)(BTC)2(H2O)6中,TPT的三个位点全部配位,电荷分布均匀,没有极化现象。分子极化导致了电子云的排布的差异使得光致变色性能发生改变。对于化合物Zn(TPT)(BTC)H2O中未配位的吡啶基,进行相关化学修饰方面的探索,考察相关的性能变化。
The characters of the materials are related to the constructions. In this paper, with the purpose of designing and synthesis new metal organic frameworks, we did lots of works on synthesis and characterizing. As most of synthetic reactions, template has been revealed as important factor that goven the structure, so does the MOFs. In this paper, a new two-dimensional metal organic framework is synthesized and characterized. The encapsulated chloride anions organize a collection of building units into a novel mixed-ligand metal organic supramolecular assembly, indicating specific host-guest recognition. By constrast, the addition of F-、Br-、I-、PO4- anions only give out the coordination complexes with single ligand. Reactions of the Zn2+ ion with 1,2,4-benzenetricarboxylic acid have been investigated with emphasis on the facors that govern reaction results. And the sample is characterized by the elemental analysis, TGA, XPRD, IR, and luminescent data.
In addition, the relations between the luminescence characters and constructions are also investigated.π-πstacking in the 2,4,6-tris(4-pyridyl)-1,3,5-triazine aromatic nitrogen-containing ligand and its metal-ligand complex Zn(TPT)2(H2O)4(OH)2 1 have been investigated by single-crystal X-ray diffraction analyses. The stacking mode of the ligand change from the offset conformation to a face-to-face perfect alignment with the coordination to the zinc centers. The structure features have correlated with their solid-state luminescence properties. With excited at 360nm, free TPT ligand gives a strong fluorescent emission at 455nm and the ligand-centered emission of the metal-ligand complex occurs at the same wavelength with lower emission intensity. The distance between the aromatic rings respond to the difference of the luminescence characters.
Otherwise, the MOFs could become photochromic materials based on the interesting energy transition among the moleculars.Two new mixed-ligand metal organic frameworks Zn(TPT)(BTC)H2O and Zn3(TPT)(BTC)2(H2O)6 are also synthesized and characterized. Compared with the Zn3(TPT)(BTC)2(H2O)6, Zn(TPT)(BTC)H2O displayed strong photochromic phenomenon. As in Zn(TPT)(BTC)H2O, there is a un-coordinated atom N, and the charge distribution in TPT is imbalance. Contrarily, the charge distribution in Zn3(TPT)(BTC)2(H2O)6 is symmetrical, and the difference respond to the diversity of the photochromic characters. Post modification with pyridine in Zn(TPT)(BTC)H2O also has been investigated.
引文
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