Interlocked structures based on H-bonded barbiturate complexes

Thornton, Peter James (2015). Interlocked structures based on H-bonded barbiturate complexes. University of Birmingham. Ph.D.

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Abstract

The work contained within this thesis concerns the synthesis and characterisation of novel [2]-rotaxanes, mediated via H-bonded templation. The template in question is based upon the barbiturate receptor as developed by A. D. Hamilton which up until now had not been utilised in the synthesis of interlocked structures.
The initial approaches centred on the use of long appendages of the barbiturate towards a threading, and subsequent clipping approach; however a lack of initial threading event prevented formation of the pseudorotaxane. In an attempt to overcome these difficulties, the synthesis of more rigid, dumbbell-barbiturates, were applied towards a receptor-based clipping approach, but the steric bulk acquired from the rigid spacer groups appeared to hinder any cyclisation.
To overcome the problem of threading, shorter appendages were utilised and the threading was observed via a crystal structure of the complex. Subsequent stoppering of the azideterminated appendages in a CuAAC reaction afforded the first Hamilton Receptor based [2]- rotaxane. Further studies involving bichromophoric, anthracene-terminated receptors were then utilised with these barbiturate guests in the synthesis of a [2]-rotaxane via a novel light-induced photodimerisation.

Type of Work:

Thesis (Doctorates > Ph.D.)

Award Type:

Doctorates > Ph.D.

Supervisor(s):