|Alternative Title||Single Crystal Growth, Structures Analyses and Crystallization Mechanism of Covalent Organic Frameworks|
|Thesis Advisor||王为 ; 孙俊良|
|Place of Conferral||兰州|
|Keyword||共价有机框架材料 单晶生长 结构解析 嵌套异构|
共价有机框架材料（Covalent Organic Frameworks，简称COFs）是一类新型有机多孔晶型高分子材料，由多种多样的有机小分子前体通过共价键连接而成。从2005年报道以来，COFs在气体吸附、催化、光电、储能、传感、载药等方面有着广泛的应用前景，常被认为是有机材料界的“有机分子筛”。然而，作为一种固体晶型材料，COFs的单晶一直没有被合成出来——强共价键键连、多孔性质这两大因素导致其单晶的生长极其困难。这对COFs材料的结构解析也造成巨大阻碍，很大程度上也限制了材料实际的进一步应用和长远发展。本文利用一种调制合成的方法，首次合成出COFs材料的大尺寸单晶，并利用单晶X射线衍射技术解析了COFs材料的单晶结构。在此过程中还发现了新的COFs拓扑结构（lon-b-c3）、观察到COFs的嵌套异构现象、了解了COFs的主客体化学、研究了COFs体系单晶生长的机理等。期待本工作在晶体工程、多孔材料、共价键自组装、超分子化学和主客体化学等领域能有所贡献。
Covalent organic frameworks (COFs) represents a new class of crystalline porous organic polymers, the structures of which are diversely constructed via the covalent bonding of pre-designed organic monomers. Most research in this fascinating area has been focusing on applications such as gas sorption, catalysis, photoelectricity, energy storage, sensor, drug delivery etc, then it can be served as “organic zeolites” in organic material. However, as a solid crystalline material, single crystals of COFs haven’t been obtained since the first report from 2005. In difference from hydrogen or coordination bonding, strong covalent-bonding and porosity are the significant obstacle in growing single crystals. Therefore, structure solution and reality of further application were hindered. Powder X-ray diffraction and advanced electron diffraction analyses were usually used to determine the COF structures based on reticular chemistry and topology analysis, but many of their structures are still ambiguous. In this contribution, we developed a modulator method to obtain large single-crystal COFs, and the single-crystal X-ray diffraction structures of COFs are reported here first time. In this process, a new topology of lon-b-c3 was explored, and the interpenetration isomerism in COFs was also observed. Furthermore, host-guest chemistry in COFs was confirmed. On this basis, the crystallization mechanism can be studied. We hope our work can contribute to the field of crystal engineering, porous material, covalent self-assembly, supramolecular chemistry, host-guest chemistry, and so on.
We believe our work not only breaks traditional thinking for making a covalent crystals, but also sheds new lights to the further development of COFs. These works will have profound impact on structural investigation, structure-performance relationship, and the universal acknowledge for future application of COFs.
|马天琼. 共价有机框架材料单晶的生长、结构及成晶机理研究[D]. 兰州. 兰州大学,2018.|
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