深夜福利国产精品

Team SMOM has developed Solid-state Molecular OrganoMetallic (SMOM) chemistry, a methodology that offers a new way for chemists to approach the synthesis, stabilisation and catalytic use of highly reactive transition metal complexes.

Traditionally, organometallic chemistry is performed in solution. However, solvents can cause problems by competing with weak ligands, such as alkanes, triggering decomposition or causing complexes to aggregate. 

The team has developed methods that bypass solvents entirely by using single-crystal to single-crystal (SC鈥揝C) solid鈥揼as reactivity. As they put it, 鈥渋f the problem is the solvent, the solution is to remove the solvent鈥�.

Some of the advantages that the SMOM approach brings to synthesis and catalysis are:

• Solvent-free 鈥榠n crystallo鈥� reactions: by conducting organometallic reactions entirely in the solid state and exposing precursor crystals to reactive gases, such as hydrogen, ethene or propene, SC鈥揝C transformations become possible. Small gas molecules diffuse into the crystal lattice, react with the metal centres and form new complexes while the bulk material retains crystallinity. This allows precise structural characterisation using single-crystal X-ray diffraction, including in situ gas cell experiments at Diamond Light Source, as well as 3D electron diffraction and solid-state NMR spectroscopy before, during and after the reaction.
  
  
• Capturing complexes that are unstable in solution: because no solvent is used, the SMOM approach can isolate and crystallographically characterise exceptionally reactive and weakly bound organometallic complexes that would otherwise decompose or undergo ligand displacement in solution. This is illustrated by the isolation of sigma-alkane transition metal complexes, in which transition metal cations bind directly to simple alkanes such as propane or norbornane via three-centre, two-electron bonds.
  
  
• Solid-state confinement effects: a key feature of SMOM systems is the use of weakly coordinating anions, most notably tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. These large anions pack together to form a protective cage around the highly reactive, positively charged metal centre. This microenvironment stabilises the cation while providing hydrophobic pathways that allow small reactant gases to move in and out of the structure.
  
  
• Heterogeneous catalysis with molecular precision (SMOM鈥揅at): SMOM also bridges the gap between homogeneous and heterogeneous catalysis. The team has shown that these crystalline materials can act as catalysts for continuous gas鈥搒olid flow reactions, such as the efficient conversion of ethene to propene through a cascade of SMOM catalysts. Because the active catalyst is a well-defined molecular complex embedded within a lattice, the approach combines the precision of homogeneous catalysis with the practical advantages of heterogeneous systems.
  
  
• Integration of experiment and theory: a central aspect of SMOM chemistry is the integration of experimental work with advanced computational modelling. Conventional computational models, which treat systems in isolation or in solution, often fail to capture behaviour within a crystal lattice. Instead, the team uses periodic density functional theory (DFT) to model the full crystalline environment. This complements experimental X-ray and solid-state NMR data and provides insights that are not accessible experimentally. It also enables detailed mechanistic understanding, including how steric constraints imposed by the solid-state environment influence structure and stability.

One of the great strengths of the team is its complementary expertise across synthesis, organometallic chemistry, catalysis, crystallography and theory, which made it possible to tackle highly reactive systems with real depth and detail.

Antonio Martinez

Q&A

What are your feelings on receiving a Horizon Prize?

Tobias Kraemer: I am very happy that I was part of this team, and it is great to see all the great work done by this team over the years being recognised by this award.

Jack Heaton: As someone at the start of their academic journey, it means a lot to have been able to contribute something towards an outstanding team effort and be recognised alongside some remarkable colleagues.

Antonio Martinez: I am very pleased to see SMOM recognised in this way. For me, it is especially meaningful to have been part of this team during my postdoctoral time in Oxford. Looking back now, I appreciate even more that period and the collective effort behind this recognition.

Mathew Gyton: I am really excited to be part of the team receiving this prize. I had a huge amount of fun and learned an incredible amount along the way, so to have all that work recognised by others is incredibly gratifying.

Samantha Furfari: Being part of the team recognised for this substantial body of work in SMOM has been incredibly rewarding. I really valued my time as a PDRA on the project, particularly the opportunity to build my crystallography skills and to discover just how powerful ssNMR can be.

What was your role within the team?

Tobias Kraemer: I was part of the computational team, which developed the protocols and methods required to study the reactivity and dynamics of these organometallic complexes within the solid state.

Antonio Martinez: I was part of the experimental side of the team, contributing through work on sigma-alkane chemistry, early catalytic applications and flow studies with gas feedstocks, alongside synthetic and crystallographic studies.

What were the biggest challenges in this project, and how did you overcome them?

Antonio Martinez: One of the biggest challenges was working with highly reactive systems while translating batch solid-state gas chemistry into flow catalysis. We overcame this by developing an in-house built flow reactor that allowed monitoring under variable gas feed conditions.

Mathew Gyton: One of the most challenging problems we ever had was trying to make a deuterium-labelled analogue of one of the complexes being studied. This needed a deuterated superacid, and we kept losing deuterium content. I will never forget the day we realised that it was because of the glass, which, even though rigorously dry, still had enough surface water to ruin our isotope labelling experiments. Luckily, we could solve this by modifying the surface of our glass, but it was still one of the most technically precise chemical reactions I have ever had to do.

What different strengths did different people bring to the team?

Antonio Martinez: One of the great strengths of the team is its complementary expertise across synthesis, organometallic chemistry, catalysis, crystallography and theory, which made it possible to tackle highly reactive systems with real depth and detail.

Why is SMOM chemistry so important and exciting?

Samantha Furfari: The SMOM approach has enabled a much deeper understanding of 蟽-alkane complexes and, as a result, the mechanisms of C鈥揌 bond activation. This insight is crucial for the rational design of metal complexes capable of activating methane and converting what is currently a waste product into something more valuable. Over many years, work from the team has demonstrated how the microenvironment can both stabilise alkane ligands and induce regioselectivity in alkane binding, closely mimicking the behaviour observed in enzymatic systems.

How might the team's findings be used in real-life applications?

Mathew Gyton: These projects started out as fundamental research that are now really looking to translate into making positive changes to the world. When I think back to my time working with hyperpolarised NMR applications, it is exciting to consider the possibilities of using this chemistry to make a real impact in medical imaging.

How important would you say collaboration is for producing high-quality science? How has collaboration influenced your work?

Simon Coles: Collaboration is absolutely fundamental to how the National Crystallography Service operates to help address the toughest crystallography-related problems, and our relationship with the SMOM team has deepened over the years such that we work together from writing proposals through to producing journal articles.

Tobias Kraemer: Close collaboration between experiment and theory is nowadays essential to tackle the complexity of many chemical systems. Quantum chemical calculations provide detailed insight into mechanistic and spectroscopic properties of a system and, in many cases, can help with the interpretation of experimental data. It is this dialogue between theory and experiment that really drives these projects and enables true synergies between them.

Antonio Martinez: Collaboration is indeed central to this work and to science more broadly, because highly reactive systems like these cannot really be understood through a single technique or perspective. For me, being part of SMOM reinforced how much stronger the science becomes when colleagues from different areas work closely together.

Matthew Gyton: I feel that much of this work would be almost impossible without collaboration from each expert recognised. When I think about the projects I contributed to as a synthetic chemist, there was input from theoreticians, spectroscopists and crystallographers that elevated the quality and success of the work far beyond what each of us could individually accomplish. 

What does good research culture mean to you, and why does it matter?

Simon Coles: Balanced leadership creates a culture and environment where everyone is equal, feels able to contribute, and knows that those contributions are valued.

Antonio Martinez: An environment where people are supported, valued and challenged. It is important because strong science depends not only on good ideas and results, but also on trust, respect and working together.

Matthew Gyton: A good research culture is all about enabling everyone around you to succeed, individually and as a team, irrespective of whether they are junior or senior to you. Scientists who feel valued and supported will themselves reach out and support others. I strongly believe the rising tide really does lift all boats. 

In what ways does creativity influence how you think about or carry out your work?

Antonio Martinez: For me, creativity is part of the enjoyment of doing research, solving problems and turning unexpected results into new research directions.

Matthew Gyton: A lot of the research I have contributed to has been one big problem-solving adventure, chasing that key experiment to nail the result, and this is where creativity has been critical. As a Lego kid, I have not met a chemistry problem I could not solve with a creative piece of glassware or an afternoon with the Swagelok catalogue. 

What do you wish more people understood about your field or the chemical sciences in general?

Kris Altus: The chemical sciences, in my opinion, largely go under the radar among the broader population. A lot of chemistry is not flashy or easily relatable compared to other sciences. However, chemistry is at the heart of many day-to-day consumer products, such as transport fuels, pharmaceuticals and plastics, as well as the food and beverage industry. The advances we make in fundamental knowledge now may impact the public and the products we consume in the future. It is therefore important that we keep pushing the boundaries of chemical knowledge to advance the production of these products in a sustainable and efficient way that supports modern society.

Thinking back to earlier in your career, are there any words of wisdom that you wish someone had told you?

Samantha Furfari: This is something I took away from my time working with Andy, and I wish I had heard it much earlier in my career. During a conversation about my aspirations while I was on my third PDRA, I realised that I had assumed becoming a PI was the only way to make a meaningful difference in academia. Andy helped me challenge that assumption, reshaped my career path, and ultimately led me to my current role as an education-focused lecturer, where I feel able to support and positively influence undergraduate students in tangible ways, something I value deeply.