Bringing the 4th Dimension to Chemical Crystallography - Time Resolved Photocrystallography

Lead Research Organisation: University of Bath
Department Name: Chemistry

Abstract

The importance of knowing the structure of a material to atomic resolution, the number and nature of the connectivities between the atoms, is fundamental in understanding the properties of the material. X-ray crystallography is the best method of obtaining the detailed structure of solid materials, and provides a 3D picture of the structure. However, until now, it is a technique that only looks as molecules in their ground (unreactive) state. In this proposal, for the first time, we wish to introduce the dimension of time into the crystallographic experiment. By combining the X-ray experiment with a synchronised light source, that activates the molecules into an excited (reactive) state, we will look at the structures of species with lifetimes of microseconds or even nanoseconds. To achieve this we need to build protective molecular cages around these photoreactive molecules, and to compare their solid state behaviour with what occurs in solution using time resolved IR techniques.

Publications

10 25 50
 
Description We have developed methods of using crystallography and synchrotron radiation to bring time into single crystal X-ray diffraction experiments. We have studied linkage isomers and characterised their metastable states, and also incorporated the linkage isomers into MOF hosts to improve their switching properties when exposed to light.
Exploitation Route Others are now using the time-resolved crystallographic methods that we have developed to study short-lived materials under photoactivation.
Sectors Chemicals,Education,Electronics,Energy

 
Description EPSRC
Amount £140,929 (GBP)
Funding ID EP/G067759/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 10/2009 
End 09/2013
 
Description EPSRC
Amount £140,929 (GBP)
Funding ID EP/G067759/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 09/2009 
End 08/2013
 
Description EPSRC
Amount £673,215 (GBP)
Funding ID EP/D072859/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 10/2006 
End 09/2011
 
Description EPSRC
Amount £673,215 (GBP)
Funding ID EP/D072859/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 10/2006 
End 08/2011
 
Description EPSRC
Amount £1,735,643 (GBP)
Funding ID EP/I01974X/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 03/2011 
End 08/2016
 
Title Methods for determining the structures of materials that are metastable or have short lifetimes in the solid state using photocrystallographic methods 
Description We have developed single-crystal X-ray crystallographic methods for determining the structures of metastable materials using photocrystallographic methods. These methods have been adopted by other groups and photocrystallography is now a growing topic. 
Type Of Material Improvements to research infrastructure 
Year Produced 2010 
Provided To Others? Yes  
Impact We have established the structures of a range of coordination complexes that show linkage isomerism under photoactivation. The use of LEDs to photoactivate the materials is now in teh public domain and the methodology has been adopted by a number of research groups.