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Metal-Organic Frameworks for the Structure Determination of Non-Crystalline Compounds via the Crystalline Sponge Method

Habib, Faiza; (2022) Metal-Organic Frameworks for the Structure Determination of Non-Crystalline Compounds via the Crystalline Sponge Method. Doctoral thesis (Ph.D), UCL (University College London). Green open access

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Abstract

In this thesis, the most commonly studied crystalline sponge [{(ZnI2)3(tris(4-pyridyl)-1,3,5-triazine)2·x(CHCl3)}n] (1) was used to produce three novel complexes. The structure of three terpenes namely farnesol, geraniol and β-damascone were determined in the pores of sponge 1. Despite being the most successful crystalline sponge 1, has a few limitations such as exhibiting a hydrophobic pore environment, small pore size and instability in the presence of polar solvents and nucleophiles. Literature MOFs were searched for alternative crystalline sponges to overcome these limitations. The MOF {[Co2(L)(H2O)3]·(solvent)x}n L = bis-(3,5-dicarboxy-pheny1)terephthalamide (3) was investigated as an alternative crystalline sponge and studies resulted in two novel complexes with 3-phenylpropanol and 2-phenylethanol. In sponge 3 guest binding occurred via hydrogen bonding and the hydrophilic pore environment was suitable to accommodate polar solvents. Another literature MOF {[Cd7(BTA)4(H2O)(DMF)]·(solvent)x}n BTA = 4,4’4’’-[1,3,5-benzenetriyltris(carbonylimino)]-trisbenzoic acid (4) was also investigated as an alternative crystalline sponge. Due to different synthetic procedures being used, a new structure of the MOF 4 was developed and that was used in subsequent studies. Sponge 4 outperformed sponge 1 in terms of stability and was stable in the presence of polar aprotic, polar protic solvents and Lewis bases. Inclusion complexes with the solvents, acetonitrile, acetone, and isopropanol demonstrated a hydrophilic pore environment where these guest molecules were fixed via hydrogen bonding. In contrast, pyridine was accommodated in sponge 4 via the coordinative alignment method (CAL). This observation led to the generation of five novel inclusion complexes with 4-aminopyridine, 3,5-lutidine, 3-bromopyridine, 4-acetylpyridine and 4,4’-bipyridine, which were accommodated in 4 via CAL. Another investigation was made to compare the closely similar structures of sponge 4 and pyridine derived sponge 4’. N,N-dimethylaniline and propiophenone were accommodated in the pores of both the sponges and the differences in the host-guest interactions were studied. In the inclusion complexes of 4 and 4’ with N,N-dimethylaniline hydrogen bonding was not observed as the dominant host-guest interaction.

Type: Thesis (Doctoral)
Qualification: Ph.D
Title: Metal-Organic Frameworks for the Structure Determination of Non-Crystalline Compounds via the Crystalline Sponge Method
Open access status: An open access version is available from UCL Discovery
Language: English
Additional information: Copyright © The Author 2022. Original content in this thesis is licensed under the terms of the Creative Commons Attribution-NonCommercial 4.0 International (CC BY-NC 4.0) Licence (https://creativecommons.org/licenses/by-nc/4.0/). Any third-party copyright material present remains the property of its respective owner(s) and is licensed under its existing terms. Access may initially be restricted at the author’s request.
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/10158735
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