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Towards interlocked structures based on H-bonded barbiturate complexes

Rocher, Mathias (2010)
Ph.D. thesis, University of Birmingham.

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Abstract

Despite the privileged position of Hamilton’s barbiturate binding system in supramolecular chemistry, this motif has never been used in generating interlocked structures, such as rotaxanes or catenanes. This thesis demonstrates the feasibility of such structures. A series of Hamilton-like receptors has been synthesised. Their conversion from “open” to “closed” forms by metathesis and their binding with barbital was studied, demonstrating the importance of the macrocycle size. Barbiturates disubstituted with flexible chains terminated either by reacting groups (anthracenes, olefins) or stoppers (trityl) were also synthesised. The fluorescence properties of anthracene-tagged barbiturates and their kinetics of intramolecular anthracene photodimerisation and thermal return were studied, demonstrating remarkable differences depending on the chain length. Binding studies of these barbiturates with the receptors were then undertaken, revealing smaller binding constants compared with barbital. A series of ring-closing experiments involving the barbiturate complexes was then undertaken, either by anthracene photodimerisation or olefin metathesis. In one metathesis experiment, indirect evidence for the formation of a low amount of catenane was obtained by mass spectrometry, where the smallest ring is formed by a chain of only 19 carbon atoms, which is unprecedented. Finally, different synthetic pathways for the synthesis of barbiturates substituted with large rigid substituents were investigated. Models of their complexes with the receptors and IR studies are presented that suggest that their structure would facilitate the formation of interlocked complexes.

Type of Work:Ph.D. thesis.
Supervisor(s):Tucker, James
School/Faculty:Colleges (2008 onwards) > College of Engineering & Physical Sciences
Department:School of Chemistry
Subjects:QD Chemistry
Institution:University of Birmingham
ID Code:868
This unpublished thesis/dissertation is copyright of the author and/or third parties. The intellectual property rights of the author or third parties in respect of this work are as defined by The Copyright Designs and Patents Act 1988 or as modified by any successor legislation. Any use made of information contained in this thesis/dissertation must be in accordance with that legislation and must be properly acknowledged. Further distribution or reproduction in any format is prohibited without the permission of the copyright holder.
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