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Details of Grant 

EPSRC Reference: GR/T03352/01
Title: New Synthons fir Light-Switchable Molecular Devices: Synthesis and Photophysical Insight
Principal Investigator: Weinstein, Professor JA
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Humboldt University Berlin
Department: Sch of Chemistry
Organisation: University of Nottingham
Scheme: Standard Research (Pre-FEC)
Starts: 01 December 2004 Ends: 31 January 2005 Value (£): 178,199
EPSRC Research Topic Classifications:
Chemical Biology Chemical Synthetic Methodology
EPSRC Industrial Sector Classifications:
Chemicals Healthcare
Pharmaceuticals and Biotechnology
Related Grants:
Panel History:
Panel DatePanel NameOutcome
21 Apr 2004 Chemistry Fellowships Interview Panel 2004 Deferred
18 Mar 2004 Chemistry Fellowships Sift Panel 2004 Deferred
Summary on Grant Application Form
Light to chemical energy conversion lies in the heart of many natural processes and applications. The key intermediate in most of these processes is a charge-separated excited state. The issue of vital importance is how to control stability of this excited state, stabilizing it mainly towards back electron transfer. I have developed a conceptually new approach to this issue, namely, to use the formation of a transient sulfur-sulfur bond S\S in the excited state of metal chromophores as a tool to stabilize charge separation. At the core of this approach lie metal thiolate complexes with the transition metal acting as a conducting spacer. These systems are highly advantageous as a core building block in systems for utilization of the energy of light because (i) they are synthetically feasible and easily modifiable, (ii) the S\S bond allows the properties of the excited state relevant to the specific applications to be tuned via modification of the ligands and/or metal. We will design, synthesize and explore [L-M-thiolate] units, where M(II) = Pt, Pd, L = diimine or cyclometallated ligands, such as thyenyl-pyridine and derivatives. To achieve charge separation, thiolates will be modified by electron donors (e.g., phenothiazine, PTZ), and L - by electron acceptors (viologens, 4,4'-R2-4,4'-bpy). The reduced form of viologen and the oxidized form of PTZ both have intense absorbances in the visible region. This will allow us to monitor the dynamics of the exited states by Time-Resolved (TR) Absorption Spectroscopy, and TR InfraRed, Emission and Raman spectroscopy, where applicable. The rate of electron transfer will be derived as a function of the free energy, the distance and the stability of the SAS bond, obtained from theoretical calculations. This study will lead to new synthons for supramolecular chemistry with directional electron and/or energy transfer, and advance a fundamental understanding of light-induced processes.
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Organisation Website: http://www.nottingham.ac.uk