Time Resolved Crystallography

Lead Research Organisation: University of Bath
Department Name: Chemistry

Abstract

Single crystal X-ray diffraction is the most powerful method available for determining the three dimensional structure of molecular materials in the solid state. However, it has always been viewed as a ground state, time averaged method of analysis that does not give information on what molecules look like when they are undergoing a chemical or photochemical reaction. This project sets out to change this situation, and introduce the 4th dimension of time into diffraction experiments so that it will be possible to determine the structure of molecules as they undergo a photochemical activation and see species that have lifetimes of a few microseconds of less. Using this technique it will be possible to make a molecular movie and watch molecular geometries change, in three dimensions, as the chemical process occurs. In order to undertake a successful time resolved (photocrystallographic) experiment it is necessary to pump the crystal with a pulsed laser and probe it with an X-ray beam from a synchrotron in a synchronised fashion so that the excited state structure is obtained.This has the potential to be a very important technique for understanding the processes that occur in opto-electronic materials when they are activated, and may help in the designe of new smart materials.

Publications

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Bajwa S (2012) On the appearance of nitrite anion in [PdX(OAc)L2] and [Pd(X)(C^N)L] syntheses (X = OAc or NO2): photocrystallographic identification of metastable Pd(?1-ONO)(C^N)PPh3 in Chemical Science

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Bou-Moreno R (2011) Systematic structural studies on cobalt(II) complexes of tricyclohexylphosphine oxide and related ligands in Polyhedron

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Brayshaw S (2011) Coordination Behavior and Transformations of Thienyl-Substituted Diacetylenes upon Coordination to Os 3 H 2 (CO) 10 in Organometallics

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Brayshaw S (2010) Photocrystallography - design and methodology for the use of a light-emitting diode device in Journal of Applied Crystallography

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Brayshaw SK (2011) Highly efficient visible-light driven photochromism: developments towards a solid-state molecular switch operating through a triplet-sensitised pathway. in Chemistry (Weinheim an der Bergstrasse, Germany)

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Buntem R (2010) A Density Functional Theory Investigation on Intramolecular Hydrogen Transfer of the [Os 3 (CO) 11 P(OMe) 3 (Ru(? 5 -C 5 H 5 )) 2 ] Cluster in Bulletin of the Korean Chemical Society

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Burrows A (2012) The effect of carboxylate and N,N'-ditopic ligand lengths on the structures of copper and zinc coordination polymers in CrystEngComm

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Cotton S (2008) Synthesis and structure of a dimeric scandium bis(µ-methoxy) complex in Inorganic Chemistry Communications

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Cotton S (2017) Systematics and surprises in lanthanide coordination chemistry in Coordination Chemistry Reviews

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Cotton SA (2022) The Synthesis and Structure of a Scandium Nitrate Hydroxy-Bridged Dimeric Complex Supported by Bipyridyl Ligands. in Molecules (Basel, Switzerland)

 
Description We have discovered how to use X-ray crystallography to "watch" chemical processes as they occur. In the method called photocrystallography the materials are activated by light and time-resolved crystallographic methods are used to determine the structure of the molecules in their excited states which may only exist for microseconds. These materials can act as switches and sensors, changing color under photoactivation.
Exploitation Route The work in this Fellowship has led on to subsequent grants and a current Programme Grant. This research has developed the area further. Other academic groups are now using the methods that we have developed, and several industrial companies are interested in the materials for real world applications.
Sectors Chemicals,Education,Electronics,Energy,Healthcare
 
Description Methods for studying materials under photoactivation were developed. These are now being looked at by industry so see if the promising materials could be used as sensors and switches.
First Year Of Impact 2011
Sector Electronics,Energy
Impact Types Economic
 
Description EPSRC
Amount £108,403 (GBP)
Funding ID EP/F021151/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 10/2008 
End 09/2012
 
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.