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.
Organisations
People |
ORCID iD |
Paul Robert Raithby (Principal Investigator) |
Publications
Warren MR
(2014)
Solid-state interconversions: unique 100 % reversible transformations between the ground and metastable states in single-crystals of a series of nickel(II) nitro complexes.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Warren MR
(2009)
Reversible 100% linkage isomerization in a single-crystal to single-crystal transformation: photocrystallographic identification of the metastable [Ni(dppe)(eta1-ONO)Cl] isomer.
in Angewandte Chemie (International ed. in English)
Towrie M
(2009)
A time-resolved infrared vibrational spectroscopic study of the photo-dynamics of crystalline materials.
in Applied spectroscopy
Raithby P
(2007)
Small-molecule chemical crystallography-from three to four dimensions: a personal perspective
in Crystallography Reviews
Howard JA
(2009)
Trans-cinnamic acid and coumarin-3-carboxylic acid: experimental charge-density studies to shed light on [2 + 2] cycloaddition reactions.
in Acta crystallographica. Section B, Structural science
Brayshaw SK
(2012)
Photocrystallographic identification of metastable nitrito linkage isomers in a series of nickel(II) complexes.
in Dalton transactions (Cambridge, England : 2003)
Brayshaw S
(2010)
Photocrystallography - design and methodology for the use of a light-emitting diode device
in Journal of Applied Crystallography
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 | £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 |
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 | £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 | 08/2011 |
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. |