The project has covered most of the goals originally proposed and create new and exciting opportunities built on the control gained on the assembly of porous, ultrastable molecular frameworks.
New synthetic platforms in Reticular Chemistry: we have implemented high-throughput synthetic methodologies for the systematic preparation of titanium-organic frameworks. These families of MOFs – labelled as MUV (Materials of University of Valencia)– are based on earth abundant metals and combine sizeable porosities with exceptional chemical stabilities. These synthetic routes have led to new strategies for the chemical engineering of photocatalytic activity of porous solids (Angew. Chem. Int. Ed. 2018, 57, 8453–8457), the introduction of siderophore-type linkers as alternative metal connectors for engineering photocatalytic performance (J. Am. Chem. Soc. 2019, 141, 13124–13133), the assembly of photoactive mesoporous solids with surface areas beyond 2000 m2·g-1 (Chem. Sci. 2019, 10, 4313–4321), or the design of the first family of permanently porous titanium-organic cages (J. Am. Chem. Soc. 2021, 143, 21195–21199). We have also introduced new concepts to enable dual-metal synergistic catalysis in heterometallic MOFs (Chem 2020, 6, 3118–3131) or the use of cluster chemistry for selective implantation of amines for cooperative catalysis in porous solids (Angew. Chem. Int. Ed. 2021, 60, 11868–11873).
Chemical complexity for targeted function: we have also set focus in advancing our understanding on how the composition or spatial arrangement of MOF components or defects can determine their function. In this context, we have developed new methodologies for the synthesis of heterometallic titanium-organic frameworks by unprecedented metal-induced dynamic topological transformations (J. Am. Chem. Soc. 2020, 142, 6638–6648), or demonstrated the effect of linker distribution in the photocatalytic activity of multivariate mesoporous crystals (J. Am. Chem. Soc. 2021, 143, 1798–1806). We have also pioneered alternative routes for controlling the introduction of defects in titanium MOFs by using modulators with varying connectivity (Chem. Sci. 2020, 12, 2586–2593) or sub-stochiometric linker concentrations (Chem. Sci. 2021, 12, 11839–11844), and have demonstrated the advantages offered by fine control of the metal distribution in mixed-metal MOFs for accessing unprecedented mixed oxide catalysts (Chem Catal. 2021, 1, 364–382).
Processing at the nanoscale for device integration: conductive MOFs and bi-stable coordination polymers are carving a niche for themselves in the world of molecular electronics. The tunability and processability of these materials alongside with the combination of electrical conductivity with porosity or spin transition offers unprecedented opportunities from their integration into functional devices. We have achieved the fabrication of MOF ultrathin films for the design of electronically active interfaces (J. Am. Chem. Soc. 2016, 138, 2576–2584), study of the electrical response of MOF devices featuring films as thin as 10 nm (Adv. Mater. 2018, 30, 1704291), or the development of instrumentation for demonstrating the origin of the chemo resistive response of MOF films to changes in the environment (Angew. Chem. Int. Ed. 2018, 57, 15086–15090). In the context of spin transition, we have has also demonstrated the influence of pillaring linkers on the vertical charge transport of ultrathin films of 2D Hofmann-type clathrates (Chem. Mater. 2019, 31, 7277–7287), or the effect of nanostructuration on their spin crossover transition (Chem. Sci. 2019, 10, 4038–4047). Most of our contributions in this context have been covered in a topical review of the area (Chem. Soc. Rev. 2020, 49, 5601–5638).
Exploitation of results: Some of the technologies and materials created during the project have led to the creation of 2 start-ups: Porous Materials for Advanced Applications S. L. (2018) and Porous Materials in Action S. L. (2021), to accelerate the transfer of these results into products and services. These entrepreneurial platforms have licensed one of the patents filed during the project to approach the high-scale synthesis of MOFs with optimal cost and reduced environmental impact to enable their commercialization. This has already facilitated the signature of transfer contracts with several technological centers and companies.
