通过固体核磁共振研究小分子晶体材料的结构与分子运动

发布时间：2018-01-15 05:17

本文关键词：通过固体核磁共振研究小分子晶体材料的结构与分子运动　出处：《华东师范大学》2017年博士论文　论文类型：学位论文

【摘要】：从分子层面研究晶体材料的结构与分子运动对理解其宏观性能具有重要的实际意义。围绕这一课题,本文将利用一系列先进的固体核磁共振技术,包括:静态2HNMR、13C化学位移各向异性(CSA)线形分析等,研究一系列小分子晶体材料的结构以及分子运动。探讨这些微观性质与材料宏观性能的联系。论文的主要内容如下:(1)对MOF晶体(HIm)2[KCo(CN)6](HIm=咪唑阳离子)中HIm阳离子的分子运动进行了研究:通过固体2H NMR揭示了 HIm阳离子在两次相变过程中不同的运动行为。通过1HNMR揭示了材料中HIm阳离子在相转变过程中的质子解离现象。基于上述结果,探讨了 HIm阳离子的分子运动与该材料宏观介电转变之间的关系。(2)对小分子晶体二(2-氯乙基)胺盐酸盐中二(2-氯乙基)胺(BCEA)阳离子的分子运动进行了研究:通过固体2H NMR揭示了 BCEA阳离子发生了轴向旋转;结合2H NMR和13C CSA线形分析,实现了 BCEA阳离子旋转轴的确定。基于上述结果,探讨了 BCEA阳离子的旋转运动与该材料宏观介电转变之间的关系。(3)对MOF晶体(HPy)2[Na(H20)2Co(CN)6](HPy=吡啶阳离子)中HPy阳离子的分子运动进行了研究:通过固体2HNMR和13CCSA线形分析对HPy阳离子的分子运动进行了分析。研究了晶体框架与HPy阳离子之间的氢键对HPy阳离子分子运动的调控作用,探讨了氢键对该材料介电转变的影响。(4)对 MOF 晶体(MA)2[B'Co(CN)6](MA=甲基胺阳离子,B'=Na,K,Rb)中MA阳离子的分子运动进行了分析。研究了晶体框架大小对MA阳离子分子运动的影响,探讨了如何通过调整晶体框架大小实现对材料相转变的调节。(5)对小分子晶体[CH6N3]2[FeK2(H20)6CN6]([CH6N3]=胍阳离子)的固-固相转变进行了研究。通过1H NMR对晶体的失水与再水合过程进行了原位观测。基于上述核磁结果,探讨了该材料中固-固相转变的分子机理。综上,本论文通过一系列先进的固体核磁共振技术揭示了一些小分子晶体材料的结构与分子运动,探讨了分子运动与宏观性能之间的关系。本论文工作充分展示了现代核磁共振技术在晶体结构表征和分子运动研究中的独特的优势。本论文的研究结果有助于我们从分子层面理解材料宏观性能的来源,同时对新型功能材料的结构设计提供了可努力的方向。
[Abstract]:It has important practical significance for understanding the macroscopic properties from the molecular level structure and molecular motion of crystal materials. Around this topic, this paper will use a series of advanced solid-state NMR techniques, including: static 2HNMR, 13C chemical shift anisotropy (CSA) linear analysis, a series of small molecule crystal materials the structure and molecular motion. To investigate the macroscopic properties of these microscopic properties and materials. The main contents of this paper are as follows: (1) of MOF crystal (HIm) 2[KCo (CN) 6] (HIm= imidazolium cations) molecular motion of HIm cations were studied: the motion behavior of HIm cation in two different times during the phase change process 2H NMR revealed by solid. By 1HNMR revealed that the HIm cation material on the phase transition of proton dissociation phenomena in the process. Based on the above results, to explore the molecular motion of HIm cations and the macroscopic dielectric materials The relationship between the change. (2) of small molecule crystal two (2- chlorine ethyl) amine hydrochloride (two 2- chlorine ethyl) amine (BCEA) molecular motion cations were studied by solid state 2H NMR revealed that BCEA cations in axial rotation; combination of 2H NMR and 13C CSA linear analysis, the determination of BCEA cation of the rotation axis. Based on the above results, discusses the relationship between the change of rotational motion of BCEA cations and the material macroscopic dielectric. (3) crystal of MOF (HPy) 2[Na (H20) 2Co (CN) 6] (HPy= HPy cationic pyridinium cation) molecular motion is studied by solid 2HNMR and 13CCSA analysis of linear molecular motion of HPy cations were analyzed. Studied the regulation effect between crystal framework and HPy cation of hydrogen bond on HPy cation molecular motion, to investigate the effect of hydrogen bonding on the dielectric transition. (4) crystal of MOF (MA) 2[B'Co (CN) 6] (M A= methyl amine cation B'=Na, K, Rb), molecular motion of MA cations were analyzed. The effect of crystal size on the framework of MA cationic molecular motion, discusses how to adjust the frame size by adjusting the crystal phase transformation of materials. (5) of small molecular crystals [CH6N3]2[FeK2 (H20) (6CN6] [CH6N3]= guanidinium cation) solid solid phase transition was studied. By 1H NMR on the crystal water and re hydration process were observed in situ. The NMR results based on molecular mechanism of solid solid phase change in the material. In this paper, through a series of advanced solid-state NMR technique reveals some small the molecular crystal structure and molecular motion, to explore the relationship between molecular motion and macroscopic properties. This work shows the modern NMR study on crystal structure and molecular motion in the The research results in this paper will help us understand the source of macroscopical properties of materials from molecular level, and provide a direction for the structural design of new functional materials.

【学位授予单位】：华东师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O641.4;O482.532

【相似文献】