Research – Funimat

“New synthetic platforms for new materials”

Metal-organic frameworks (MOF) and polyhedra (MOP) are crystalline, molecular solids built from the linking of organic and inorganic components with coordinative bonds. We design and produce our own families of MOFs and MOPs based on earth abundant metals to combine sizeable porosities and exceptional chemical stability for applications of environmental relevance. They are labelled as MUV (Materials of the Universidad de Valencia). Check some of them out:

MUV-10

Chemical Engineering of Photoactivity in Heterometallic Titanium–Organic Frameworks by Metal Doping

Angew. Chem. Int. Ed. 57, 8453–8457 (2018).

MUV-11

Hydroxamate Titanium–Organic Frameworks and the Effect of Siderophore-Type Linkers over Their Photocatalytic Activity.

J. Am. Chem. Soc. 141, 13124–13133 (2019).

cMUV-11

Permanent Porosity in Hydroxamate Titanium–Organic Polyhedra.

J. Am. Chem. Soc. 143, 21195–21199 (2021).

MUV-101

Heterometallic Titanium-Organic Frameworks as Dual-Metal Catalysts for Synergistic Non-buffered Hydrolysis of Nerve Agent Simulants.

Chem 6, 3118–3131 (2020).

MUV-12

Selective Implantation of Diamines for Cooperative Catalysis in Isoreticular Heterometallic Titanium–Organic Frameworks.

Angew. Chem. Int. Ed. 60, 11868–11873 (2021).

MUV-12(X) and MUV-12(Y)

Isoreticular expansion and linker-enabled control of interpenetration in titanium–organic frameworks.

J. Am. Chem. Soc., 145, 21397–21407 (2023).

“Chemical complexity for targeted function”

The use of Metal-Organic Frameworks as crystalline matrices for the synthesis of multiple component or multivariate solids by the combination of diferent linkers or metals into a single material has emerged as a versatile route to tailor the properties of single-component phases or even access new functions. We are also interested in advancing our understanding of how the composition or spatial arrangement of MOF components can determine their function or behavior. Please check some of our works for further info:

Heterometallic Titanium–Organic Frameworks by Metal-Induced Dynamic Topological Transformations

J. Am. Chem. Soc. 142, 6638–6648 (2020).

Effect of Linker Distribution in the Photocatalytic Activity of Multivariate Mesoporous Crystals.

J. Am. Chem. Soc. 143, 1798–1806 (2021)

Unlocking mixed oxides with unprecedented stoichiometries from heterometallic metal-organic frameworks for the catalytic hydrogenation of CO2

Chem Catal. 1, 364-382 (2021)

Tetrazine Linkers as Plug‐and‐Play Tags for General Framework Functionalization and C60 Conjugation

Angew. Chem. Int. Ed. 61, e202208139 (2022)

Metal Node Control of Brønsted Acidity in Heterobimetallic Titanium–Organic Frameworks

J. Am. Chem. Soc. 10.1021/jacs.2c12718 (2023)

Chemical complexity for targeted function in heterometallic titanium-organic frameworks

Chem. Sci., 14, 6826-6840 (2023).

Wrapping up Metal-Organic Framework Crystals with Carbon Nanotubes

Adv. Func. Mater., 2302246 (2023).

“Biodesign in crystalline frameworks”

Metal-organic Frameworks are versatile platforms compatible with the use of biological components as amino acids, peptides, nucleobases or enzymes, either as components or functional guests. Compared to other porous materials, the recognition, interaction or structural response of these biomolecules can be precisely tuned with the pore chemistry of MOFs. Check some of our recent advances in this context:

Peptide Metal–Organic Frameworks for Enantioselective Separation of Chiral Drugs

J. Am. Chem. Soc. 139, 4294–4297 (2017).

Translocation of enzymes into a mesoporous MOF for enhanced catalytic activity under extreme conditions.

Chem. Sci. 10, 4082–4088 (2019).

Homochiral Metal–Organic Frameworks for Enantioselective Separations in Liquid Chromatography

J. Am. Chem. Soc. 141, 14306–14316 (2019)

Crystalline supramolecular organic frameworks via hydrogen-bonding between nucleobases

Chem. Commun. 57, 1659–1662 (2021)

“Processing at the nanoscale for device integration”

Materials scientists are currently shifting from purely inorganic, organic and silicon-based materials towards hybrid organic–inorganic materials to develop increasingly complex and powerful electronic devices. In this context, it is undeniable that conductive Metal–Organic Frameworks and bistable coordination polymers are carving a niche for themselves in the electronics world. The tunability and processability of these materials alongside the combination of electrical conductivity with porosity or spin transition offers unprecedented technological opportunities for their integration into functional devices. See some of our works in this context:

High-Quality Metal–Organic Framework Ultrathin Films for Electronically Active Interfaces

J Am Chem Soc 138, 2576–2584 (2016)

Origin of the Chemiresistive Response of Ultrathin Films of Conductive Metal–Organic Frameworks.

Angew. Chem. Int. Ed. 57, 15086–15090 (2018)

Bottom-Up Fabrication of Semiconductive Metal–Organic Framework Ultrathin Films

Adv. Mater. 30, 1704291 (2018)

Electrical conductivity and magnetic bistability in metal–organic frameworks and coordination polymers: charge transport and spin crossover at the nanoscale

Chem. Soc. Rev. 49, 5601–5638 (2020)

On-Surface Design of a 2D Cobalt-Organic Network Preserving Large Orbital Magnetic Moment

J. Am. Chem. Soc. 144, 16034-16041 (2022)

“Photoreactivity in porous materials”

Applications of titanium-organic frameworks in photocatalysis are continuously expanding due to the unique properties that can arise from the combination of high surface area, crystallinity good photostability and photoactivity. Moreover, compared to traditional inorganic semiconductors as TiO2, their photocatalytic activity can be finely tuned by engineering the nature and distribution of the organic and inorganic components in the framework. Recommended works for more info:

Chemical Engineering of Photoactivity in Heterometallic Titanium–Organic Frameworks by Metal Doping

Angew. Chem. Int. Ed. 57, 8453–8457 (2018).

Hydroxamate Titanium–Organic Frameworks and the Effect of Siderophore-Type Linkers over Their Photocatalytic Activity.

J. Am. Chem. Soc. 141, 13124–13133 (2019).

De novo synthesis of mesoporous photoactive titanium(IV)–organic frameworks with MIL-100 topology.

Chem. Sci. 10, 4313–4321 (2019).

Effect of Linker Distribution in the Photocatalytic Activity of Multivariate Mesoporous Crystals

J. Am. Chem. Soc. 143, 1798–1806 (2021).

“Defect chemistry as a synthetic tool”

The recognition of defect chemistry as a true synthetic tool for targeted creation of defects and controllable performance remains limited by the pool of frameworks explored. The value of defect engineering in controlling the properties of defective frameworks has been beautifully exemplifed and largely demonstrated with UiO-type materials based on Zr(IV) nodes. We aim to extend this chemistry to a broader range of inorganic clusters to exploit the rich chemical and structural versatility ofered by other families of MOFs.

Effect of modulator connectivity on promoting defectivity in titanium–organic frameworks

Chem Sci 12, 2586–2593 (2020).

Linker depletion for missing cluster defects in non-UiO metal–organic frameworks

Chem Sci 12, 11839–11844 (2021).

Synthetic control of correlated disorder in UiO-66 frameworks

Nat. Commun., 14, 6962 (2023).