Please use this identifier to cite or link to this item: https://hdl.handle.net/10356/145860
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dc.contributor.authorLi, Liuxiaoen_US
dc.date.accessioned2021-01-12T07:57:40Z-
dc.date.available2021-01-12T07:57:40Z-
dc.date.issued2020-
dc.identifier.citationLi, L. (2020). Synthesis and topology control of covalent organic frameworks. Doctoral thesis, Nanyang Technological University, Singapore.en_US
dc.identifier.urihttps://hdl.handle.net/10356/145860-
dc.description.abstractAs a class of crystalline porous materials which are built by organic building units, covalent organic frameworks (COFs) are attracting tremendous attention in recent decades. Because of their intrinsic properties of porous, high stability, and low density, this kind of material has drawn great attention in the fields of sensing, catalysis, and gas storage/separation, etc. Topology or crystal structure which is determined by the pore size and shape is one of the most important parameters of COFs. Therefore, this thesis aims to controlled synthesize COFs with novel topologies and explore their application in AIE, drug delivery, and controlled CO releasing. First, a series of 2D COFs with kgd topology, namely HFPB-TAPA, HFPB-TAPB, and HFPB-TABPB are synthesized via solvothermal reaction of HFPB and TAPA, TAPB, TABPB, respectively. The as-prepared 2D COFs constructed from monomers with C6 and C3 symmetry form micropores. As a proof of concept application, HFPB-TABPB with micropores is selected as the drug carrier for drug loading and releasing of ibuprofen (with a size of 6 x 12 Å). Second, by altering substituents of the building block with the same symmetry, two highly crystalline phase-pure 2D COFs, namely TPE-COF-OH and TPE-COF-OMe, with different topologies and porosities were successfully synthesized and characterized. Low-dose HRTEM imaging combined with molecular simulation indicates that the linkage conformations of the COF skeletons governed by intramolecular hydrogen bonding dictate the resulting COF topologies. Additionally, benefit from the abundant existence of (N, O)-bidentate Schiff base moieties in TPE-COF-OH, post-synthetic modifications of TPE-COF-OH to form a boron complexation, namely TPE-COF-BF2, fluorescence “turn on” and “aggregation-induced emission” properties of the obtained TPE-COF-BF2 were also observed. Last, a new porous 3D COF, denoted as TamBpyda was developed via the condensation of (2, 2′-Bipyridine)-5, 5′-dicarboxaldehyde (BPyDA) and tetra (4-anilyl)methane (TAM). The as-prepared TamBpyda was further metalated with Mn(CO)5Br to generate manganese carbonyl complex functionalized Mn-TamBpyda. As a proof-of-concept application, Mn-TamBpyda was applied as the CO releasing materials, which exhibited the ability to deliver and release CO inside the cells upon the light irradiation.en_US
dc.language.isoenen_US
dc.publisherNanyang Technological Universityen_US
dc.rightsThis work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License (CC BY-NC 4.0).en_US
dc.subjectEngineering::Materialsen_US
dc.titleSynthesis and topology control of covalent organic frameworksen_US
dc.typeThesis-Doctor of Philosophyen_US
dc.contributor.supervisorZhang Qichunen_US
dc.contributor.schoolSchool of Materials Science and Engineeringen_US
dc.description.degreeDoctor of Philosophyen_US
dc.identifier.doi10.32657/10356/145860-
dc.contributor.supervisoremailQCZHANG@ntu.edu.sgen_US
item.grantfulltextembargo_20230110-
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