Periodic Reporting for period 2 - SupraVox (Metal-Oxide Polymerization Chemistry: From Molecular Vanadium Oxide Monomers to Supramolecular Oligomers and Polymers)
Reporting period: 2023-10-01 to 2025-03-31
The ERC CoG Project SUPRAVOX studies the formation of inorganic, metal oxide based oligomers and polymers from functional monomeric materials. To-date, state-of-the-art metal oxide chemistry lacks the ability to predictably design materials and their properties from the atomic level upwards. This ability, however, would provide ultimate control over metal oxide structure and reactivity, giving access to next-generation functional materials. Societal challenges in areas including information technology, sustainable energy and public health could thus be addressed by knowledge-based materials design. In addition, understanding the supramolecular chemistry which governs bottom-up metal oxide aggregation will provide fundamental insights into spontaneous structural organization and the rise of complexity in prebiotic chemistry. SUPRAVOX develops bottom-up vanadium oxide polymerization chemistry as a new design paradigm to bridge the gap between molecular building blocks and solid-state metal oxides. This will lead to a new class of materials, where novel chemical and electronic properties become accessible by atomically precise assembly of designer monomers. SUPRAVOX develops molecular vanadium oxide monomers with tuneable structure, composition and linkage chemistry as models for industrially important metal oxides. SUPRAVOX lays the synthetic and mechanistic foundations for metal oxide polymerization chemistry as a new paradigm for the controlled, bottom-up design of advanced nanostructured metal oxides with impact on global technologies including battery materials, electrocatalysis and sensing.
Within the first 30 months of the project, ground-breaking discoveries for the design, synthesis and functionalization of vanadium oxide monomers and oligomers have been made. First, we have developed a range of new monomeric materials where physical and electronic structures, chemical reactivity and size can be controlled by chemical-synthetic means.
Building on these new materials, we have studied mechanistic details of monomer formation to rationalize future synthetic developments. Design of Experiment statistical methodologies have been applied to the complex synthesis to identify the key experimental parameters by a principal component analysis approach.
Also, we have explored initial phases of monomer-to-dimer and monomer-to-oligomer linkage using in situ and ex situ analytical experimental methods.
In addition to these experimental studies, we are now embarking on theoretical analyses also which we will use as benchmarks to gain further insight into experimental analyses. To-date, this has resulted in 7 peer-reviewed publications which summarize the main findings and breakthroughs from the project to-date.
Building on these new materials, we have studied mechanistic details of monomer formation to rationalize future synthetic developments. Design of Experiment statistical methodologies have been applied to the complex synthesis to identify the key experimental parameters by a principal component analysis approach.
Also, we have explored initial phases of monomer-to-dimer and monomer-to-oligomer linkage using in situ and ex situ analytical experimental methods.
In addition to these experimental studies, we are now embarking on theoretical analyses also which we will use as benchmarks to gain further insight into experimental analyses. To-date, this has resulted in 7 peer-reviewed publications which summarize the main findings and breakthroughs from the project to-date.
In the following areas, we have made breakthrough discoveries which will impact on the development of the field and beyond:
New synthetic routes to molecular vanadium oxide monomers, including the use of redox-equilibration and coupled light/dark reaction equilibria to form these species.
In situ characterization of reactivity and intermediates by spectroscopic and spectrometric methods
Use of supramolecular symmetry driven templating effect of organic species to control structure and electronic properties of vanadium oxides.
Until the end of the project, I expect further advances in the areas of:
Size-dependent effects on electronic structure of vanadium oxide oligomers and polymers
Control of electrochemical and photochemical reactivity
Theoretical predictability of reaction modes dependent on vanadium oxide monomer structure
New synthetic routes to molecular vanadium oxide monomers, including the use of redox-equilibration and coupled light/dark reaction equilibria to form these species.
In situ characterization of reactivity and intermediates by spectroscopic and spectrometric methods
Use of supramolecular symmetry driven templating effect of organic species to control structure and electronic properties of vanadium oxides.
Until the end of the project, I expect further advances in the areas of:
Size-dependent effects on electronic structure of vanadium oxide oligomers and polymers
Control of electrochemical and photochemical reactivity
Theoretical predictability of reaction modes dependent on vanadium oxide monomer structure