Synthesis of rotaxanes and pseudorotaxanes as intermediates towards molecular cages

Weske, Damian Franz (2013). Synthesis of rotaxanes and pseudorotaxanes as intermediates towards molecular cages. University of Birmingham. Ph.D.

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Abstract

The work described in this thesis concerns the synthesis of novel rotaxanes and pseudorotaxanes as intermediates towards molecular cages. The area of rotaxanes and cage molecules was reviewed and selected examples discussed in detail.

Three main strategies to synthesise a fumaramide thread were investigated, however these were unsuccessful. By changing the templating station and the stopper groups, several novel azo-dicarboxylate threads were synthesised, as well as their [2]- and [3]rotaxanes. Unusual reductions of the azo-dicarboxylate stations during the clipping processes were observed and these were studied in detail.

A couple of different stopper groups from those initially used, provided several novel double fumaramide threads and rotaxanes in high yields

Linking reactions of the two macrocycles of the newly synthesised [3]rotaxanes to form a molecular cage were investigated. However, reduction of the macrocycles was required, which led to deslipping of the macrocycles. Therefore, new routes to generate rotaxanes with bulkier stopper groups were explored.

In the final section, novel pseudorotaxanes were synthesised and detected via \(^1\)H NMR spectroscopy and mass spectrometry. By linking the two macrocycles of a [3]pseudorotaxane, a molecular cage was formed.

Type of Work:

Thesis (Doctorates > Ph.D.)

Award Type:

Doctorates > Ph.D.

Supervisor(s):