An investigation of alternative separation strategies for common chemical mixtures by means of host-guest chemistry protocols with host compounds N,N′- bis(5-phenyl-5-dibenzo[a,d]cycloheptenyl)ethylenediamine and N,N’-bis(5-phenyl-10,11- dihydro-5-dibenzo[a,d]cycloheptenyl)ethylenediamine

Abstract

In this work, the selectivity behaviour of two host compounds, namely N,N’-bis(5-phenyl-5- ibenzo[a,d]cycloheptenyl)ethylenediamine (H1) and N,N’-bis(5-phenyl-10,11-dihydro-5- ibenzo[a,d]cycloheptenyl)ethylenediamine (H2), was assessed in mixtures of difficult-toseparate compounds, including the xylenes and ethylbenzene, pyridine and methylpyridines, and anisole and methylanisoles. These host compounds were synthesized using Grignard addition reactions with phenylmagnesium bromide on dibenzo[a,d]cyclohepten-5-one and 10,11- dihydrodibenzo[a,d]cyclohepten-5-one, respectively. The resultant alcohols were treated with perchloric acid to form the corresponding perchlorate salts, which were then reacted with ethylenediamine to afford the required H1 and H2 host compounds. Yields were 95 ad 52% for this final step in each case. An investigation of the conformations, both from experiment (using single crystal X-ray diffractometry (SCXRD) on the apohost compound) and computational calculations was undertaken. Unfortunately, H1 always crystallized out as a powder unless this host compound formed a complex with a guest species, and so could not be subjected to SCXRD analysis as apohost alone. However, a single crystal structure for apohost H2 was successfully obtained and compared with computational data from a previous investigation. It was observed that the conformation of apohost H2 compared favourably with that of the lowest energy conformer from that work. In single solvent recrystallization experiments with o-, m-, p-xylene (o-Xy, m-Xy, p-Xy) and ethylbenzene (EB), both H1 and H2 formed complexes with only one of the four guest species, namely p-Xy and o-Xy, respectively. The host:guest (H:G) ratios were 1:1 for both of these complexes. In the equimolar guest/guest competition experiments, inclusion complexes only formed when p-Xy or o-Xy, respectively, were present in the mixtures; if p-Xy (for experiments with H1) or o-Xy (H2) was absent from these mixtures, only apohost was recovered from the glass vessels. Three selectivity profiles were constructed for each of these host compounds, in which each one was recrystallized from binary mixed guests in various proportions. These demonstrated an overwhelming preference of H1 for p-Xy and H2 for o-Xy, which concurred with the results from the equimolar experiments. Thermal analysis using H1∙p-Xy revealed that this complex was unstable at ambient conditions, while SCXRD explained this observation: this complex may be defined as a true clathrate since no host‧‧‧guest interactions were identified at all, and the guest was retained in the complex by means of steric factors alone. Furthermore, the guest molecules resided in wide open channels that may have facilitated the guest release process. H2∙o-Xy, on the other hand, was stable at room temperature, and the guest release event only commenced at 69.7 °C (Ton). This too was explained by SCXRD analyses in that interactions between host and guest species were observed in this case. Additionally, the guest molecules were housed in discrete cages, which made their escape more challenging compared with p-Xy in H1∙p-Xy. It was concluded that, in this guest series, both of the host compounds would be effective as separatory tools employing host-guest chemistry protocols due to their remarkable selectivities for p-Xy (H1) and o-Xy (H2).Thesis (MSc) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 202