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.
Organisations
People |
ORCID iD |
Paul Robert Raithby (Principal Investigator) |
Publications
Bou-Moreno R
(2011)
Systematic structural studies on cobalt(II) complexes of tricyclohexylphosphine oxide and related ligands
in Polyhedron
Brayshaw S
(2010)
Photocrystallography - design and methodology for the use of a light-emitting diode device
in Journal of Applied Crystallography
Brayshaw S
(2011)
Coordination Behavior and Transformations of Thienyl-Substituted Diacetylenes upon Coordination to Os 3 H 2 (CO) 10
in Organometallics
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)
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
Burrows A
(2012)
The effect of carboxylate and N,N'-ditopic ligand lengths on the structures of copper and zinc coordination polymers
in CrystEngComm
Chan L
(2022)
Structural diversity in the series of lanthanide complexes [Ln(Ph3PO)n(NCS)3] (n = 3, 4)
in Polyhedron
Cotton S
(2017)
Systematics and surprises in lanthanide coordination chemistry
in Coordination Chemistry Reviews
Cotton S
(2008)
Synthesis and structure of a dimeric scandium bis(µ-methoxy) complex
in Inorganic Chemistry Communications
Cotton SA
(2022)
The Synthesis and Structure of a Scandium Nitrate Hydroxy-Bridged Dimeric Complex Supported by Bipyridyl Ligands.
in Molecules (Basel, Switzerland)
De La Riva H
(2006)
A new type of luminescent alkynyl Au4Cu2 cluster.
in Inorganic chemistry
Harford PJ
(2012)
Expanding the tools available for direct ortho cupration--targeting lithium phosphidocuprates.
in Dalton transactions (Cambridge, England : 2003)
Hatcher L
(2011)
Metastable Linkage Isomerism in [Ni(Et 4 dien)(NO 2 ) 2 ]: A Combined Thermal and Photocrystallographic Structural Investigation of a Nitro/Nitrito Interconversion
in Angewandte Chemie International Edition
Hatcher L
(2014)
Dynamic single-crystal diffraction studies using synchrotron radiation
in Coordination Chemistry Reviews
Hatcher LE
(2013)
Solid-state photochemistry of molecular photo-switchable species: the role of photocrystallographic techniques.
in Acta crystallographica. Section C, Crystal structure communications
Johnson AL
(2009)
Unprecedented double migratory insertion of phenyl isocyanide into cyclopentadienyl C-H bonds.
in Dalton transactions (Cambridge, England : 2003)
Jones M
(2010)
Cu(II) homogeneous and heterogeneous catalysts for the asymmetric Henry reaction
in Journal of Molecular Catalysis A: Chemical
Kondo Y
(2007)
On the Kinetic and Thermodynamic Reactivity of Lithium Di(alkyl)amidozincate Bases in Directed Ortho Metalation
in Journal of the American Chemical Society
Li P
(2008)
A new series of dinuclear Au(I) complexes linked by diethynylpyridine groups.
in Dalton transactions (Cambridge, England : 2003)
Mole RA
(2011)
Two stage magnetic ordering and spin idle behavior of the coordination polymer Co3(OH)2(C4O4)2·3H2O determined using neutron diffraction.
in Inorganic chemistry
Moskalenko A
(2009)
Nanomechanical electron shuttle consisting of a gold nanoparticle embedded within the gap between two gold electrodes
in Physical Review B
Nahar S
(2010)
Routes to Higher Nuclearity Mixed-Metal Carbonyl Clusters Using the [Rh(?5-C5Me5)(NCMe)3]2+ Dication as a Building Block
in Journal of Cluster Science
Pérez Y
(2011)
Synthesis of complexes with the polydentate ligand N,N'-bis(2-hydroxyphenyl)-pyridine-2,6-dicarboxamide
in Polyhedron
Shah HH
(2013)
New multi-ferrocenyl- and multi-ferricenyl- materials via coordination-driven self-assembly and via charge-driven electro-crystallization.
in Inorganic chemistry
Sudha Devi L
(2009)
Synthesis and Comparison of the Optical Properties of Platinum(II) Poly-ynes with Fused and Non-Fused Oligothiophenes
in Macromolecules
Tong L
(2008)
Supramolecular Assemblies of Tripodal Porphyrin Hosts and C 60
in Chemistry - A European Journal
Tong LH
(2011)
Complexes of aryl-substituted porphyrins and naphthalenediimide (NDI): investigations by synchrotron X-ray diffraction and NMR spectroscopy.
in Dalton transactions (Cambridge, England : 2003)
Torres-Sandoval I
(2010)
Reaction of the diyne complex [Os3(µ-CO)(CO)9{µ3-?2-Me3SiCCCCSiMe3}] with phosphines and phosphites: Characterization of monophosphine substituted clusters [Os3(µ-CO)(CO)8(PR3){µ3-?2-Me3SiCCCCSiMe3}] (PR3=PPh3, P(OEt)3, PEt3, PHPh2 and Ph2PCH2PPh2)
in Journal of Organometallic Chemistry
Towrie M
(2009)
A time-resolved infrared vibrational spectroscopic study of the photo-dynamics of crystalline materials.
in Applied spectroscopy
Warren J
(2009)
A prototype environmental gas cell for in situ small-molecule X-ray diffraction
in Journal of Applied Crystallography
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)
Willcocks AM
(2011)
Bis(tert-butyl isocyanide-?C)[4-fluoro-N-({2-[N-(4-fluorophenyl)carboximidoyl]cyclopenta-2,4-dien-1-ylidene}methyl)anilinido-?2N,N']copper(I).
in Acta crystallographica. Section C, Crystal structure communications
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. |