Hayes, Lilian M.; (2017) Porous Complexes for the Unambiguous Structural Determination of Non-Crystalline Compounds. Doctoral thesis , UCL (University College London).

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Abstract

The ability of the metal-organic framework (MOF) [{(ZnI2)3(tris(4-pyridyl)-1,3,5-triazine)2(solvent)}n] (1) to act as a so-called ‘crystalline sponge’ for the analysis of non-crystalline compounds via single-crystal X-ray diffraction has be assessed. A variety of guest-encapsulation studies have been performed to investigate the most reliable protocol for its synthesis, the scope of guest encapsulation and the guest-host interactions formed. Repeat encapsulation experiments demonstrated the reproducibility of the technique and that guest molecules take up specific sites within the unit cell consistently albeit with minor variations in orientation and disorder. Systematic studies of guest-host interactions were subsequently undertaken to develop an understanding of the crystalline sponge and how it displays such unique properties of guest ordering. Analysis of encapsulation compounds with chemically related guests showed many sites within the unit cell are consistently favourable, governed by π···π and CH···π interactions. A minority of positions are taken up by guests only of specific functionality, through the formation of specific guest-host and guest-guest aromatic interactions, van der Waals interactions and hydrogen bonds. Parallel work has sought to develop alternative crystalline sponges through reticular synthesis for the encapsulation of guest molecules of variable steric requirement. Three organic compounds based on the functionality of tris(4-pyridyl)-1,3,5-triazine (used in 1) have been synthesised using Stille and Suzuki coupling reactions. Together they form an isoreticular series of potential linkers with similar functionality and chemical whilst displaying systematic increases in size. Work focused on developing solvothermal and/or interfacial synthesise to produce novel MOFs in single-crystalline form for future use as crystalline sponges.

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