Crystallisation kinetics of organic compounds; quinacridone derivatives as UV-active probes of solution state pre-nucleation phenomena

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dc.contributor.advisor Moynihan, Humphrey A. en
dc.contributor.author Shanahan, Louise
dc.date.accessioned 2019-06-05T08:27:36Z
dc.date.issued 2019
dc.date.submitted 2019
dc.identifier.citation Shanahan, L. 2019. Crystallisation kinetics of organic compounds; quinacridone derivatives as UV-active probes of solution state pre-nucleation phenomena. PhD Thesis, University College Cork. en
dc.identifier.uri http://hdl.handle.net/10468/8012
dc.description.abstract An ideal crystallisation process is predictable and reproducible; a less than simple ask. The influence of pre-nucleation molecular interactions in solution on the crystallised phase obtained has been highlighted. To improve our understanding of crystallisation outcomes, comprehending solution-state pre-nucleation phenomena is desirable. Previously, the aggregation of di- and tetra(alkoxy) derivatives of quinacridone 1 has been studied in solution using UV-vis spectroscopy: λmax shifts were observed for certain derivatives under conditions of increased concentration or reduced temperature. Correlation of IR spectra of aggregates in solution, with phases of unsubstituted quinacridone 1 in the solid-state, led to proposed structures of these species in solution. The scope of the previous work in this area was herein extended to a wider range of alkoxyquinacridones and solvents including: 2-MeTHF, NMP, DMF and DMSO. Tetra(alkoxy)quinacridones featuring pentyloxy, octyloxy, dodecyloxy, elaidyloxy or oleyloxy chains, as well as 2,9-di-(2-undecyltridecyl-1-oxy)quinacridone, were prepared as probes of molecular interactions in solution. Analysis of these compounds by UV-vis spectroscopy revealed concentration and temperature dependent bathochromic shifts in solvents such as 2-MeTHF and toluene. Aggregation was found to be solvent, concentration, temperature and substrate dependent. Aggregation of tetra(alkoxy)-quinacridones in 2-MeTHF was modulated by addition of hydrogen bonding competing solvents such as NMP. Other highlights of the work include the selective acquisition of various phases of quinacridone 1 from N,N’-disubstituted quinacridones, with MEM or SEM removable groups. Distinctive solid-state forms of 2,3,9,10-tetra(dodecyloxy)quinacridone were also obtained, distinguished by colour and IR spectroscopy, as well as unusual disparity in their 1H NMR spectra. We also report a novel synthesis of unsubstituted quinacridone 1 and N,N’- dialkylated quinacridones, employing aryne chemistry. Representing a mild preparation, the sterically un-hindered target, N,N’-dimethylquinacridone, was obtained in particularly high yield applying this methodology. Full abstract can be viewed on https://cora.ucc.ie/bitstream/handle/10468/8012/Abstract.pdf?sequence=1&isAllowed=y en
dc.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher University College Cork en
dc.rights © 2019, Louise Shanahan. en
dc.rights.uri http://creativecommons.org/licenses/by-nc-nd/3.0/ en
dc.subject Quinacridones en
dc.subject Solvatochromic compounds en
dc.subject Solution-state aggregation en
dc.subject Solid-state forms en
dc.title Crystallisation kinetics of organic compounds; quinacridone derivatives as UV-active probes of solution state pre-nucleation phenomena en
dc.type Doctoral thesis en
dc.type.qualificationlevel Doctoral en
dc.type.qualificationname PhD en
dc.internal.availability Full text not available en
dc.description.version Accepted Version
dc.contributor.funder Science Foundation Ireland en
dc.description.status Not peer reviewed en
dc.internal.school Chemistry en
dc.check.type No Embargo Required
dc.check.reason This thesis is due for publication or the author is actively seeking to publish this material en
dc.check.opt-out Yes en
dc.thesis.opt-out true
dc.internal.conferring Summer 2019 en
dc.internal.ricu Analytical and Biological Chemistry Research Facility en


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