Development of novel supramolecular framework materials based on organic salts

Wahl, Helene (2014-12)

Thesis (PhD)--Stellenbosch University, 2014.

Thesis

ENGLISH ABSTRACT: The aim of the work presented in this thesis was to design ionic organic framework materials based on carboxylate salts with the intention of engineering interesting properties, such as porosity, into these framework materials. The first section focuses on the characterisation and porosity studies of an ionic framework material, 3,4-lutidinium pamoate hemihydrate, with THF-filled channels in the solid state. It was shown that this framework is able to exchange the THF in the channels for a wide variety of compounds, with many of these exchanges occurring in a single-crystal to single-crystal fashion. Competition experiments conducted with the framework, both by immersing crystals of the framework in solvent mixtures, as well as by exposing crystals of the framework to mixtures of solvent vapours, indicated that it is able to selectively exchange for one guest over another. The kinetics of exchange of this framework were studied, and it was possible to identify a kinetic model describing this process. A second novel framework-type material, 4-phenylpyridinium pamoate, was identified during the course of this study, as well as five isostructural frameworks containing different guest molecules. In this case the framework consists of discrete units that close-pack in such a way that guest molecules are included in constricted cavities in the solid state. Although this framework-type material is not porous, it is thermally quite stable and also highly selective. It is able to selectively encapsulate 1,4-dioxane when crystallised from various solvent combinations including 1,4-dioxane. In addition, eight novel structures with pamoic acid in combination with various pyridyl derivatives were obtained. A third novel framework material was obtained with N,N'-bis(glycinyl)pyromellitic diimide in which, due to the extended hydrogen-bonded network formed between the constituents of the framework, DMF molecules are aligned in channels. It was found that this framework material can also be formed by mechanochemical synthesis, and investigation of the thermal behaviour of this framework showed that it has the potential to be porous, since the framework appears to remain intact after desolvation. Furthermore, six novel structures with N,N'- bis(glycinyl)pyromellitic diimide in combination with various N-heterocycles were obtained. All structures obtained in this study were also further analysed to determine whether there are particular structural features that are required for framework formation. Insights gained from these investigations, in terms of degree of ionisation of the anion, packing arrangements and hydrogen bonding patterns as well as the molecular shape of the components are discussed.

AFRIKAANSE OPSOMMING: Die doel van die werk wat in hierdie tesis voorgelê word is om ioniese organiese raamwerkmateriale gebaseer op karboksilaatione te ontwerp, met die voorneme om interessante eienskappe in hierdie materiale te bewerkstellig. Die eerste afdeling fokus op die karakterisering en porositeit van ‘n ioniese organiese raamwerkmateriaal, 3,4-lutidiniumpamoaathemihidraat, wat kanale gevul met tetrahidrofuraan (THF) besit. Dit is aangetoon dat dit moontlik is vir hierdie raamwerkmateriaal om die THF in die kanale te verruil vir ‘n wye verskeidenheid stowwe, waarvan baie van hierdie uitruilings geskied as ‘n enkelkristal tot enkelkristal transformasie. Kompetisie-eksperimente is met hierdie raamwerkmateriaal uitgevoer deur die kristalle in mengsels van oplosmiddels te onderdompel, sowel as deur die kristalle aan mengsels van die oplosmiddeldampe bloot te stel. Die resultate het aangedui dat dit moontlik is vir hierdie raamwerkmateriaal om een gasstof selektief teenoor ‘n ander te verruil vir die THF in die kanale. Die kinetika van die uitruilingsproses van hierdie materiaal is ook bestudeer en dit was moontlik om ‘n kinetiese model te identifiseer wat die uitruilingsproses beskryf. ‘n Tweede nuwe raamwerk-tipe materiaal, 4-fenielpiridiniumpamoaat, is deur die loop van hierdie studie geïdentifiseer, sowel as vyf isostrukturele raamwerkmateriale waarvan net die gasstof verskil. In hierdie geval bestaan die raamwerk uit diskrete eenhede wat op so ‘n wyse saampak dat die gasstowwe in vernoude porieë ingesluit word. Alhoewel hierdie raamwerk-tipe materiaal nie poreus is nie, is dit termies stabiel en ook hoogs selektief. Die raamwerkmateriaal kan selektief 1,4-dioksaan enkapsuleer wanneer dit gekristalliseer word vanuit ‘n verskeidenheid oplosmiddel kombinasies met 1,4-dioksaan. Verder is agt nuwe strukture verkry met die pamoaat ioon in kombinasie met ‘n verskeidenheid piridien-derivate. ‘n Derde nuwe raamwerkmateriaal is verkry met N,N'-bis(glisiniel)piromellitiese diïmied waarin, danksy die uitgebreide waterstofgebinde netwerk tussen die komponente van die raamwerk, die DMF molekules in kanale aangetref word. Hierdie raamwerkmateriaal kan deur meganochemiese sintese berei word en verdere ondersoek na die termiese gedrag van hierdie raamwerkmateriaal dui aan dat dit die potensiaal het om porositeit te toon, aangesien die raamwerk behoue bly nadat die DMF molekules verwyder is. Ses nuwe strukture is ook met N,N'-bis(glisiniel)piromellitiese diïmied in kombinasie met ‘n wye verskeidenheid stikstof-bevattende heterosikliese verbindings verkry. Alle strukture wat tydens hierdie studie verkry is, is verder ondersoek om te bepaal of daar spesifieke strukturele kenmerke is wat benodig word vir die vorming van raamwerkmateriale. Insigte wat verkry is vanuit hierdie ondersoeke, in terme van die graad van ionisasie van die anioon, die rangskikking van molekules in die struktuur en waterstofbindingspatrone, sowel as die molekulêre vorm van die komponente, word bespreek.

Please refer to this item in SUNScholar by using the following persistent URL: http://hdl.handle.net/10019.1/95858
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