Complex-bearing Metal-Organic Frameworks: Snapshots of Reactions
Lead Research Organisation:
University of Nottingham
Department Name: Sch of Chemistry
Abstract
The ability to precisely determine molecular structure lies at the heart of chemistry. Often, understanding the structure of a molecule gives invaluable insight into the properties and reactivity of that molecule. However, many reactions proceed so rapidly that the determination of the three-dimensional structure of a molecule, particularly short-lived intermediates, can be enormously challenging if not impossible using conventional approaches. For many years single crystal X-ray diffraction has provided the primary methodology for determining molecular structure, but the technique is limited by the requirement for a single crystal, a crystal without, or nearly without, flaws. It is not always possible to obtain a single crystal of some molecular species, for example if a compound is highly reactive, produced in small quantities or simply does not adopt the well-ordered arrangements required for single crystals. This proposal seeks to address these issues.
We will use metal-organic frameworks (MOFs), framework structures that provide ordered structural arrangements of molecular building-blocks, as a platform for trapping and supporting metal complexes that are able to undergo subsequent reactions - all in a crystalline phase. It is possible to prepare such systems such that metal complexes, including systems that mimic compounds used in catalytic processes, sit upon the struts of the framework and are positioned next to channels that allow transport of reagents to the reactive metal site. The supported complexes can then undergo reactions without losing the overall crystallinity of the framework, allowing determination of the structure of the products. As the reactive site is protected from other molecules, embedded with the framework structure, it is possible to control which molecules are introduced to the reactive framework-supported complex and to preclude reactive sites coming together. In this way it is possible to effectively trap reactive species within the framework, allowing determination of their structures. This project will develop this strategy providing us with a method to take 'snapshots' of molecular reactions.
We will use metal-organic frameworks (MOFs), framework structures that provide ordered structural arrangements of molecular building-blocks, as a platform for trapping and supporting metal complexes that are able to undergo subsequent reactions - all in a crystalline phase. It is possible to prepare such systems such that metal complexes, including systems that mimic compounds used in catalytic processes, sit upon the struts of the framework and are positioned next to channels that allow transport of reagents to the reactive metal site. The supported complexes can then undergo reactions without losing the overall crystallinity of the framework, allowing determination of the structure of the products. As the reactive site is protected from other molecules, embedded with the framework structure, it is possible to control which molecules are introduced to the reactive framework-supported complex and to preclude reactive sites coming together. In this way it is possible to effectively trap reactive species within the framework, allowing determination of their structures. This project will develop this strategy providing us with a method to take 'snapshots' of molecular reactions.
Planned Impact
Our research directly addresses the topic of directed assembly of extended framework structures and their use in new chemistry and new materials. Therefore, our studies lie directly at the heart of the EPSRC Grand Challenge in Directed Assembly of Extended Structures with Targeted Properties, which envisages an increasingly important role for self-assembly approaches in the manufacture of new functional materials. EPSRC recognise that the time scale for these developments is uncertain and may require 20 years or even more to reach full maturity. However, we anticipate that as we develop and communicate the effectiveness of the strategy for studying reactions within complex-bearing MOFs, our approach will be taken up widely. More importantly we believe that collaborations between those directly using our approach and synthetic chemists will be become increasingly important, leading to widespread uptake of complex-bearing MOFs as a tool for elucidating and understanding reaction processes at metal complexes. We anticipate that insights into reaction processes will have short term impact on academic researchers and increasingly in the research laboratories of large companies. We will seek to develop and exploit the impact of our research through the organization of a multi-disciplinary one-day meeting for both academic and industrial parties interested in the development of this research field and the emergent strategies that we seek to develop.
The PI has a strong track record in communicating his science to wider audiences, in using the media to publicise his research and in presenting the case for science to policymakers. We believe that the proposed research is ideal for public communication and will bid to present our research at the Royal Society Exhibition in the last year of the project. A major impact from the research will be the output of trained researchers, 2 postdocs and 2 PhD students, whose training will be enhanced through their participation in a project that involves exciting international collaborations. This cohort of researchers will provide a highly significant impact, beyond the timescale of the project, through the availability of highly skilled-researchers who will support an expansion of research using tailored extended framework structures to gain insight into reaction processes. Any results of commercial significance that arise, possibly related to synthetic methodology, will be protected through the Business Partnership Unit (BPU) within the School of Chemistry at Nottingham.
The PI has a strong track record in communicating his science to wider audiences, in using the media to publicise his research and in presenting the case for science to policymakers. We believe that the proposed research is ideal for public communication and will bid to present our research at the Royal Society Exhibition in the last year of the project. A major impact from the research will be the output of trained researchers, 2 postdocs and 2 PhD students, whose training will be enhanced through their participation in a project that involves exciting international collaborations. This cohort of researchers will provide a highly significant impact, beyond the timescale of the project, through the availability of highly skilled-researchers who will support an expansion of research using tailored extended framework structures to gain insight into reaction processes. Any results of commercial significance that arise, possibly related to synthetic methodology, will be protected through the Business Partnership Unit (BPU) within the School of Chemistry at Nottingham.
People |
ORCID iD |
Neil Robert Champness (Principal Investigator / Fellow) |
Publications
Almuhana A
(2021)
Retention of perylene diimide optical properties in solid-state materials through tethering to nanodiamonds
in Journal of Materials Chemistry C
Almuhana A
(2024)
Photoinduced radical formation in hydrogen-bonded organic frameworks
in Chemical Communications
Argent SP
(2020)
Porous Metal-Organic Polyhedra: Morphology, Porosity, and Guest Binding.
in Inorganic chemistry
Boström HLB
(2024)
How Reproducible is the Synthesis of Zr-Porphyrin Metal-Organic Frameworks? An Interlaboratory Study.
in Advanced materials (Deerfield Beach, Fla.)
Griffin S
(2021)
Reactivity in Confined Spaces
Griffin S
(2020)
A periodic table of metal-organic frameworks
in Coordination Chemistry Reviews
Hassanain H
(2020)
Morpholino-Substituted BODIPY Species: Synthesis, Structure and Electrochemical Studies
in Crystals
Hassanain H
(2019)
Structural characterization and optical properties of two copper( i )-iodide BODIPY coordination polymers
in CrystEngComm
Huxley M
(2019)
Isomer Interconversion Studied through Single-Crystal to Single-Crystal Transformations in a Metal-Organic Framework Matrix
in Organometallics
Madden DG
(2022)
Densified HKUST-1 Monoliths as a Route to High Volumetric and Gravimetric Hydrogen Storage Capacity.
in Journal of the American Chemical Society
Orton GRF
(2021)
The chemistry of phosphines in constrained, well-defined microenvironments.
in Chemical Society reviews
Pearce N
(2022)
Mechanically interlocked molecular handcuffs.
in Chemical science
Pearce N
(2020)
per-Alkoxy-pillar[5]arenes as Electron Donors: Electrochemical Properties of Dimethoxy-Pillar[5]arene and Its Corresponding Rotaxane.
in Molecules (Basel, Switzerland)
Pearce N
(2020)
Electrochemical and spectroelectrochemical investigations of perylene peri-tetracarbonyl species
in Dyes and Pigments
Pearce N
(2022)
Selective photoinduced charge separation in perylenediimide-pillar[5]arene rotaxanes.
in Nature communications
Pilgrim BS
(2020)
Metal-Organic Frameworks and Metal-Organic Cages - A Perspective.
in ChemPlusChem
Robinson J
(2021)
2021 roadmap on lithium sulfur batteries
in Journal of Physics: Energy
Sweetman A
(2020)
On-surface chemical reactions characterised by ultra-high resolution scanning probe microscopy.
in Chemical Society reviews
Warfsmann J
(2021)
Thin film synthesis of hybrid ultramicroporous materials (HUMs)- a comparative approach
in Microporous and Mesoporous Materials
Young RJ
(2020)
Isolating reactive metal-based species in Metal-Organic Frameworks - viable strategies and opportunities.
in Chemical science
Young RJ
(2023)
Studying manganese carbonyl photochemistry in a permanently porous metal-organic framework.
in Chemical science
Description | The project started in 2019 but was then essentially paused during the pandemic. The researchers were able to return to the lab in the summer of 2020 and following a change of institution from the University of Nottingham to the University of Birmingham which resulted in a short delay the project has been running with little impediment part from the international collaborations which have been severely impaired. However, good progress has been made in developing new framework materials and our initial studies show considerable progress towards tethering of metal complexes to framework walls and the incorporation of metal complexes with framework pores. Publications are emerging from the award. As noted above the COVID pandemic slowed progress due to limited/restricted lab-time for those working on the grant, particularly in Nottingham. Additionally the project moved institution (Nottingham-Birmingham) which had some impact although relatively minor in comparison to the effect of the pandemic. Access to lab time has now improved and we are now working at near full capacity. Additionally the project includes significant international collaboration, including overseas visits, which have been essentially stopped due to COVID travel restrictions. |
Exploitation Route | Our studies will be of increasing importance to other fields as our results emerge and we have already begun a collaboration with organic chemists to develop our approach to important organic transformations. |
Sectors | Chemicals |
Title | CCDC 1920190: Experimental Crystal Structure Determination |
Description | Related Article: Hawazen Hassanain, E. Stephen Davies, William Lewis, Deborah L. Kays, Neil R. Champness|2019|CrystEngComm|21|4551|doi:10.1039/C9CE00845D |
Type Of Material | Database/Collection of data |
Year Produced | 2019 |
Provided To Others? | Yes |
URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc22g3m9&sid=DataCite |
Title | CCDC 1920191: Experimental Crystal Structure Determination |
Description | Related Article: Hawazen Hassanain, E. Stephen Davies, William Lewis, Deborah L. Kays, Neil R. Champness|2019|CrystEngComm|21|4551|doi:10.1039/C9CE00845D |
Type Of Material | Database/Collection of data |
Year Produced | 2019 |
Provided To Others? | Yes |
URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc22g3nb&sid=DataCite |
Title | CCDC 1920192: Experimental Crystal Structure Determination |
Description | Related Article: Hawazen Hassanain, E. Stephen Davies, William Lewis, Deborah L. Kays, Neil R. Champness|2019|CrystEngComm|21|4551|doi:10.1039/C9CE00845D |
Type Of Material | Database/Collection of data |
Year Produced | 2019 |
Provided To Others? | Yes |
URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc22g3pc&sid=DataCite |
Title | CCDC 1920193: Experimental Crystal Structure Determination |
Description | Related Article: Hawazen Hassanain, E. Stephen Davies, William Lewis, Deborah L. Kays, Neil R. Champness|2019|CrystEngComm|21|4551|doi:10.1039/C9CE00845D |
Type Of Material | Database/Collection of data |
Year Produced | 2019 |
Provided To Others? | Yes |
URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc22g3qd&sid=DataCite |
Title | CCDC 1920194: Experimental Crystal Structure Determination |
Description | Related Article: Hawazen Hassanain, E. Stephen Davies, William Lewis, Deborah L. Kays, Neil R. Champness|2019|CrystEngComm|21|4551|doi:10.1039/C9CE00845D |
Type Of Material | Database/Collection of data |
Year Produced | 2019 |
Provided To Others? | Yes |
URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc22g3rf&sid=DataCite |
Title | CCDC 1920928: Experimental Crystal Structure Determination |
Description | Related Article: Michael T. Huxley, Rosemary J. Young, Witold M. Bloch, Neil R. Champness, Christopher J. Sumby, Christian J. Doonan|2019|Organometallics|38|3412|doi:10.1021/acs.organomet.9b00401 |
Type Of Material | Database/Collection of data |
Year Produced | 2019 |
Provided To Others? | Yes |
URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc22gwfw&sid=DataCite |
Title | CCDC 1920929: Experimental Crystal Structure Determination |
Description | Related Article: Michael T. Huxley, Rosemary J. Young, Witold M. Bloch, Neil R. Champness, Christopher J. Sumby, Christian J. Doonan|2019|Organometallics|38|3412|doi:10.1021/acs.organomet.9b00401 |
Type Of Material | Database/Collection of data |
Year Produced | 2019 |
Provided To Others? | Yes |
URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc22gwgx&sid=DataCite |
Title | CCDC 1920930: Experimental Crystal Structure Determination |
Description | Related Article: Michael T. Huxley, Rosemary J. Young, Witold M. Bloch, Neil R. Champness, Christopher J. Sumby, Christian J. Doonan|2019|Organometallics|38|3412|doi:10.1021/acs.organomet.9b00401 |
Type Of Material | Database/Collection of data |
Year Produced | 2019 |
Provided To Others? | Yes |
URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc22gwhy&sid=DataCite |
Title | CCDC 1920931: Experimental Crystal Structure Determination |
Description | Related Article: Michael T. Huxley, Rosemary J. Young, Witold M. Bloch, Neil R. Champness, Christopher J. Sumby, Christian J. Doonan|2019|Organometallics|38|3412|doi:10.1021/acs.organomet.9b00401 |
Type Of Material | Database/Collection of data |
Year Produced | 2019 |
Provided To Others? | Yes |
URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc22gwjz&sid=DataCite |
Title | CCDC 1963595: Experimental Crystal Structure Determination |
Description | Related Article: Hawazen Hassanain, E. Stephen Davies, William Lewis, Deborah L. Kays, Neil R. Champness|2020|Crystals|10|36|doi:10.3390/cryst10010036 |
Type Of Material | Database/Collection of data |
Year Produced | 2020 |
Provided To Others? | Yes |
URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc23x8s3&sid=DataCite |