High Pressure Coordination Chemistry

Lead Research Organisation: University of Nottingham
Department Name: Sch of Chemistry

Abstract

We recently found that by applying high pressure to crystals of a molecule containing a palladium metal atom and three sulfur atoms caused it to polymerise into a chain. The crystal also changed colour from orange to really deep black. This happened at a pressure of around 44,000 atmospheres and we are trying to find out the reasons for the colour change by doing spectroscopic measurements and carrying out theoretical calculations. Very recently we found another molecule containing palladium and six sulfur atoms which has not one but two colour changes: as the pressure is applied the crystals of this compound first turn from blue to grey, then at higher pressure they turn from grey to orange. We are going to look at some other palladium compounds, and some with other metals such as platinum and gold, to see what happens to them under pressure.We are also going to use pressure to look at what happens to molecules inside the channels of porous compounds made from metals such as copper. These are promising candidates for the efficient storage of gases like hydrogen which could be used as clean fuel sources for cars. We need to find out how and where the molecules interact with the inner surfaces of the channels, so that we can make them into better storage containers.The high pressure experiments are done in a small pressure cell only five centimeters across and we get very high pressures just by tightening some screws. We will be doing a lot of the work the UK's newest and biggest scientific facility, the Diamond Light Source in Oxfordshire, which produces very strong X-ray beams which we fire into the crystal in the high pressure cell - this lets us work out the structure of the molecules.

Publications

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Allan DR (2014) High-pressure studies of palladium and platinum thioether macrocyclic dihalide complexes. in Acta crystallographica Section B, Structural science, crystal engineering and materials

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Henry L.S. Wong (Author) (2013) Thesis Submission by Henry L.S. Wong

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Tidey J (2014) Structural chemistry of metal coordination complexes at high pressure in Coordination Chemistry Reviews

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Tidey JP (2016) High-pressure studies of three polymorphs of a palladium(II) oxathioether macrocyclic complex. in Acta crystallographica Section B, Structural science, crystal engineering and materials

 
Description From an initial discovery [that applying high pressure to crystals of a palladium metal complex caused a number of phenomena including polymerisation and colour, geometric and conformational changes] we developed a line of research that has revealed some unprecedented effects when analogous complexes are compressed. These include pressure-induced pi-pi stacking, dramatic geometric distortion and multiple colour changes. This work has been conducted on dedicated in-house facilities supplemented by access to Diamond Light Source, the UK's synchrotron source of very bright X-rays. We expect five or six major papers to arise from this grant.
Exploitation Route Our discovery of unprecedented effects in palladium complexes has already stimulated work on other, often unrelated, metal complexes.
Our methodological developments are relevant to others doing high pressure work.
Sectors Energy,Environment

URL http://scripts.iucr.org/cgi-bin/paper?S2052520614008786
 
Description CIF funding for new high pressure crystallography laboratory
Amount £273,264 (GBP)
Funding ID CAP841 
Organisation Higher Education Funding Council for England 
Sector Public
Country United Kingdom
Start 03/2009 
End 02/2011
 
Description Core Chemistry Equipment
Amount £50,000 (GBP)
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 01/2013 
End 03/2013
 
Title Agilent Technologies Application Note on High Pressure Crystallography 
Description Non-refereed publication by A. J. Blake (Nottingham) O. Presly (Agilent) and D. R. Allan (Diamond Light Source). 
Type Of Technology New/Improved Technique/Technology 
 
Description Chair of Diamond Peer Review Panel 5 
Form Of Engagement Activity A formal working group, expert panel or dialogue
Part Of Official Scheme? No
Primary Audience Participants in your research or patient groups
Results and Impact Appointment for 2012-2014

Previously a Panel Member 2011-2012 .
Year(s) Of Engagement Activity
 
Description High-Pressure Crystallography Using Synchrotron Radiation 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Primary Audience
Results and Impact Invited lecture delivered at Department of Chemistry, University of Oxford.
Year(s) Of Engagement Activity 2011
 
Description High-Pressure Single-Crystal Diffraction Studies on the Small-Molecule Crystallography Beamline, I19, at Diamond Light Source 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience
Results and Impact Lecture.
Year(s) Of Engagement Activity 2010
 
Description Research Briefing 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Primary Audience
Results and Impact An outline of work carried out under this award was included in a presention made to EPSRC's Communications Team during a meeting hosted by Diamond Light Source on 26/2/2010.
Year(s) Of Engagement Activity 2010
 
Description Study of Palladium Thioether Complexes at High Pressure 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Participants in your research or patient groups
Results and Impact Lecture at International Union of Crystallography Congress in Madrid.
Year(s) Of Engagement Activity 2012
 
Description The Big Squeeze: High Pressure Structural Studies of Small Molecules 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Primary Audience
Results and Impact Invited Lecturer at the Organic Chemistry Institute, University of Zurich, 5 May 2009.
Year(s) Of Engagement Activity 2009
 
Description The Big Squeeze: High Pressure Structural Studies of Small Molecules 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience
Results and Impact Inaugural Research Lecture as Adjunct Professor, delivered at the Opening Ceremony for the Centre for Advanced Materials and Industrial Chemistry (CAMIC) at RMIT University, Melbourne, Australia.
Year(s) Of Engagement Activity 2012
 
Description The Big Squeeze: High Pressure Structural Studies of Small Molecules 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Primary Audience Participants in your research or patient groups
Results and Impact Invited Lecture at the Organic Chemistry Institute, University of Zurich, 5 May 2009.
Year(s) Of Engagement Activity 2009