Details of Grant 

EPSRC Reference:	EP/H048804/1
Title:	Functionalised Silicon Double Bonds
Principal Investigator:	Scheschkewitz, Dr D
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Department:	Chemistry
Organisation:	Imperial College London
Scheme:	Standard Research
Starts:	01 October 2010	Ends:	01 May 2011	Value (£):	537,398
EPSRC Research Topic Classifications:	Chemical Synthetic Methodology
EPSRC Industrial Sector Classifications:	No relevance to Underpinning Sectors
Related Grants:
Panel History:	Panel Date Panel Name Outcome 04 May 2010 Physical Sciences Panel - Chemistry Announced
Summary on Grant Application Form
In the early 1900s the idea of compounds with silicon-silicon double bonds was conceived by F.S. Kipping and publicised with the report on what we now call a disilene. While this compound later turned out to be a saturated species, this article marked the birth of organosilicon chemistry. It took until the 1980s before a genuine stable disilene was reported thus enabling thorough investigations into such compounds. Despite this late breakthrough, the quest for silicon double bonds was marked by major milestones, e.g. semiconducting polysilanes. The most prominent spin-out from the hunt for unsaturated silicon species is, however, the area of silicones (robust, still extremely flexible coatings, lubricants, plastics, etc.), which has its origins in Kipping's misconception that he had synthesised a silicon analogue of organic ketones - a silicone .An important motivating force in disilene chemistry is the resemblance of the Si=Si bond to the so-called buckled dimer terminating the surface of elemental silicon, which is used for the majority of applications of this archetypical semiconductor. The shallow potential energy surface and the resulting conformational flexibility of the Si=Si bond renders even topologically different disilenes suitable as models for the silicon surface. Disilenes replicate the weak pi-bond inherent to the buckled dimer with the small HOMO-LUMO gap and high reactivity. The application of Si=Si moieties as functional units in molecules and materials, however, remained unexplored even though such an endeavour would literally marry the concepts of classical semiconductors with that of the newly emerging organic electronics. The reason for this is readily identified in the absence of functional disilenes in the toolbox of the preparative silicon chemist. Unlike in the case of the ubiquitous alkenes that are mainly responsible for the vast diversity of Organic Chemistry, functional disilenes capable of transferring the Si=Si moiety only became readily available in 2004 by our efforts.This synthetic project will further develop the chemistry of functional disilenes. The so far most versatile transfer reagents for Si=Si moities are nucleophilic disilenides. Alternative reagents with modified reduction potential are needed to broaden their scope towards redox sensitive substrates. Electrophilic counterparts that reverse the polarity of disilenides are going to be prepared and provide access to compound classes where only nucleophilic substrates are available and/or safe to handle. After initial successes regarding the incorporation of Si=Si moieties to the periphery of pi-conjugated organic systems using disilenides, it also became quickly apparent to us that a further development of this emerging field urgently requires di- or polyfunctional derivatives, which would open the door to various applications towards supramolecular chemistry, polymer chemistry, and surface chemistry to name only a few. Our inherently molecular approach will allow us an unprecedented level of control over atomic subunits of classical semiconductors and their incorporation into organic electronics. The synthesis of a number of di- and trifunctional derivatives based on various pi-conjugated organic scaffolds will thus be pursued. To this end, conceptually novel methodologies will be developed including the use of protecting groups to carry masked functionalities through the entire length of synthetic procedures. The reactivity of these new compounds with multiple functional Si=Si moieties will be screened in comparison with that of simple disilenides.To summarise, this project will be at the forefront of the newly emerging field of an application- and property-driven chemistry of the Si=Si double bond. It will provide the synthetic tools that are ultimately expected to enable us to utilise the unique physical and chemical properties of disilenes in various applications of nanoscalar electronics.
Key Findings
This information can now be found on Gateway to Research (GtR) http://gtr.rcuk.ac.uk
Potential use in non-academic contexts
This information can now be found on Gateway to Research (GtR) http://gtr.rcuk.ac.uk
Impacts
Description This information can now be found on Gateway to Research (GtR) http://gtr.rcuk.ac.uk Summary Date Materialised
Sectors submitted by the Researcher
This information can now be found on Gateway to Research (GtR) http://gtr.rcuk.ac.uk
Project URL:
Further Information:
Organisation Website:	http://www.imperial.ac.uk