Cluster Control of Structural and Compositional diversity in Titanium-Organic frameworks

Alechania Misturini^a, Eloy Gómez-Oliveira^a, Clara Chinchilla-Garzón^a, Neyvis Almora Barrios^a, Natalia M. Padial^a, Carlos Martí-Gastaldo^a

^aFunctional Inorganic Materials team, Universidad de València, Instituto de Ciencia Molecular. c/Catedrático José Beltrán, 2 46980, Paterna, Spain

Materials for Sustainable Development Conference (MATSUS)
Proceedings of MATSUS Spring 2025 Conference (MATSUSSpring25)

Multifunctional microporous materials for advanced applications in materials science - #FunPorMat

Sevilla, Spain, 2025 March 3rd - 7th

Organizers: Pablo del Pino and Beatriz Pelaz

Invited Speaker, Carlos Martí-Gastaldo, presentation 683
DOI: https://doi.org/10.29363/nanoge.matsusspring.2025.683
Publication date: 16th December 2024

In addition to their high surface area, variability in pore size and connectivity, and compositional versatility, the ability to be modified by post-synthetic strategies has helped to tailor the properties of many families of Metal-Organic Frameworks (MOFs) to specific applications by using relatively simple methods. In this contribution, we will discuss how the use of heterobimetallic titanium clusters can enable alternative post-synthetic strategies suitable for directing structural transformations into new ultraporous architectures amenable to isoreticular design, or for integrating additional components with long-range periodicity into a pre-assembled MOF.

In 2018 we introduced a bimetallic titanium SBU, [Ti₂Ca₂(O)₂(RCO₂)₈(H₂O)₄] (Ti₂Ca₂), that combines hard (Ti⁺⁴) and soft metal sites (Ca²⁺).^[1] In addition to being compatible with the systematic design of frameworks for controllable pore dimensions and topologies,^[2] the dynamic nature of the Ca-O bonds allows integrating compositional and structural changes in the crystal whilst maintaining a periodic structure thanks to the robustness imposed by the Ti⁺⁴ nodes. This allows the preparation of crystals of MUV101 and MUV-102, heterometallic titanium MOFs isostructural to archetypical frameworks as MIL-100 and HKUST, by reaction of MUV-10(Ca) with transition metals.^[3] This metal-induced topological transformation provides control over the formation of hierarchical micro-/mesopore structures at diﬀerent reaction times and enables the formation of heterometallic titanium MOFs that are inaccessible under solvothermal conditions at high temperature, thus opening the door for the isolation of additional titanium heterometallic phases not linked exclusively bound to trimesate linkers.^[4] We will also illustrate how this combination of hard and soft coordination bonds can facilitate the translocation and ordered positioning of small molecules in these porous architectures.^[5] This is triggered by an adaptive response of the solid through a cooperative interplay between the conformational changes of the guest molecule and the reversible reconfiguration of the pore windows through the breaking/formation of coordination bonds with the Ca²⁺ sites in the framework.

References:

[1] [1] Castells-Gil, J.; Padial, N. M.; Almora-Barrios, N.; Albero, J.; Ruiz-Salvador, A. R.; González-Platas, J.; García, H.; Martí-Gastaldo, C. Chemical Engineering of Photoactivity in Heterometallic Titanium–Organic Frameworks by Metal Doping. Angew. Chem. Int. Ed. 2018, 57 (28), 8453–8457.

[2] [2] Padial, N. M.; Chinchilla-Garzón, C.; Almora-Barrios, N.; Castells-Gil, J.; González-Platas, J.; Tatay, S.; Martí-Gastaldo, C. Isoreticular Expansion and Linker-Enabled Control of Interpenetration in Titanium–Organic Frameworks. J. Am. Chem. Soc. 2023, 145 (39), 21397–21407.

[3] [3] Padial, N. M.; Lerma-Berlanga, B.; Almora-Barrios, N.; Castells-Gil, J.; Silva, I. da; Mata, M. de la; Molina, S. I.; Hernández-Saz, J.; Platero-Prats, A. E.; Tatay, S.; Martı́-Gastaldo, C. Heterometallic Titanium–Organic Frameworks by Metal-Induced Dynamic Topological Transformations. J. Am. Chem. Soc. 2020, 142 (14), 6638–6648.

[4] [4] Gómez-Oliveira, E. P.; Castells-Gil, J.; Chinchilla-Garzón, C.; Uscategui-Linares, A.; Albero, J.; Almora-Barrios, N.; Tatay, S.; Padial, N. M.; Martí-Gastaldo, C. Integrating Compositional and Structural Diversity in Heterometallic Titanium Frameworks by Metal Exchange Methods. J. Am. Chem. Soc. 2024, 146 (45), 31021–31033.

[5] [5] Rubio-Gaspar, A.; Misturini, A.; Millan, R.; Almora-Barrios, N.; Tatay, S.; Bon, V.; Bonneau, M.; Guillerm, V.; Eddaoudi, M.; Navalón, S.; Kaskel, S.; Armentano, D.; Martí-Gastaldo, C. Translocation and Confinement of Tetraamines in Adaptable Microporous Cavities. Angew. Chem. Int. Ed. 2024, 63 (30), e202402973.

Acknowledgements:

H2020 program (ERC-2021-COG-101043428), Generalitat Valenciana (PROMETEU/2021/054, MFA/2022/026) and Spanish government (PID2020-118117RB-I00 and CNS2022-135677).

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