Lusby, Paul

Leigh, David

Pike, Sarah Jane

Engineering and Physical Sciences Research Council (EPSRC)

2013-10-22T12:58:53Z

2013-10-22T12:58:53Z

2012-06-22

Over the past two decades, transitions metals have been extensively employed towards the construction (using coordination driven assembly) and operation (using reversible metal-ligand switching motifs) of supramolecular architectures. This Thesis details the investigation of an array of dynamic platinum(II)-based metallosupramolecular architectures and includes a series of model studies on switchable platinum(II) coordination modes. Chapter Two describes the synthesis and study of a series of prototype noninterlocked molecular machines. The inherent dynamics of intramolecular metalligand substitution reactions (metallotrophic shifts) are exploited to drive a d8 platinum(II-)-phenanthroline component along different ligating architectures to achieve translational (and in one case rotary) motion of the sub-molecular components. Variable temperature NMR studies of these complexes have established the kinetic parameters for the observed shuttling processes. In Chapter Three, the switchable behaviour of a metal-ligand coordination motif is reported in which a proton input is employed to modify the overall thermodynamic bias and light is orthogonally utilized to selectively lower the energetic barrier for the binding event to re-equilibration. A discussion of the light-promoted ligand exchange reaction is presented, supported by a combination of TD-DFT calculations and kinetic studies. Chapter Four describes the exploitation of this discovered pH-switchable metalligand motif for the stimuli-responsive reversible assembly of two dimensional and three dimensional metallosupramolecular architectures. Whilst Chapter Five details how this reversible motif can be exploited to induce controlled exchange between “3+1” and “2+2” square planar platinum donor sets in response to the application of acid-base stimuli.

http://hdl.handle.net/1842/7942

en

The University of Edinburgh

S. J. Pike, P. J. Lusby, Chem. Comm. 2010, 46, 8338.

P. J. Lusby, P. Müller, S. J. Pike, A. M. Z. Slawin, J. Am. Chem. Soc., 2009, 131, 16398.

transitions metals

supramolecular architectures

metal-ligand coordination

Dynamic platinum(II)- based metallosupramolecular architectures

Thesis or Dissertation

Doctoral

PhD Doctor of Philosophy