https://hdl.handle.net/10481/29458 Fri, 03 Apr 2026 22:40:54 GMT 2026-04-03T22:40:54Z https://hdl.handle.net/10481/101243 Integrating Compositional and Structural Diversity in Heterometallic Titanium Frameworks by Metal Exchange Methods. Gómez-Oliveira, Eloy P.; Castells-Gil, Javier; Chinchilla-Garzón, Clara; Uscategui-Linares, Andrés; Albero, Josep; Almora-Barrios, Neyvis; Tatay, Sergio; M. Padial, Natalia; Martí-Gastaldo, Carlos The increasing use of Metal-Organic Frameworks (MOFs) in separation, catalysis or storage is linked to the targeted modification of their composition or porosity metrics. While modification of pore shape and size necessarily implies the assembly of alternative nets, compositional changes often rely on post-synthetic modification adapted to the functionalisation or exchange of the organic linker, or the modification of the inorganic cluster by metal exchange methods. We describe an alternative methodology that enables the integration of both types of modification, structural and compositional, in titanium MOFs by metal exchange reaction of the heterometallic cluster Ti2 Ca2 . A systematic analysis of this reactivity with MUV-10 is used to understand which experimental variables are crucial to enable replacement of calcium only, or to integrate metal exchange with structural transformation. The isoreticular expanded framework MUV-30, is next used to template the formation of MUV-301, a titanium framework not accessible by direct synthesis that displays the largest mesoporous cages reported to date. Given that the interest of Ti MOFs in photoredox applications often meets the limitations imposed by the challenges of titanium solution chemistry to design concrete candidates, this soft strategy based on pre-assembled frameworks will help integrating specific combinations of metals into high porosity architectures. Submitted version https://hdl.handle.net/10481/101243 https://hdl.handle.net/10481/101167 Structural control of photoconductivity in a flexible titanium-organic framework Chinchilla-Garzón, Clara; Galbiati, Marta; Misturini, Alechania; Gimeno-Fonquernie, Pol; Almora-Barrios, Neyvis; Muñoz Padial, Natalia; Martí-Gastaldo, Carlos The soft nature of Metal-Organic Frameworks (MOFs) sets them apart from other non-synthetic porous materials. Their flexibility allows the framework components to rearrange in response to environmental changes, leading to different states and properties. Our work extends this concept to titanium frameworks, demonstrating control over charge transport in porous molecular crystals. MUV-35 is a two-fold catenated framework composed of heterometallic TiMn 2 trimers and electron donor 4,4',4''-(benzo[1,2-b:3,4-b':5,6-b'']trithiophene-2,5,8triyl)tribenzoic acid (H3 BTTTB) linkers, forming a rare sit-c net topology that can fold to reduce its volume by about 40% through a single-crystal transformation controlled by linker conformation in open, intermediate, and closed states. This process, driven by a free energy difference of nearly 300 kJ·mol-1 , originates from the formation of a continuous network of non-covalent interactions that force the spontaneous loss of the solvent in the pores of the framework to establish charge transport pathways that afford photocurrents of 2.5 × 10 -3 S·m-1 under visible light for an ON/OFF ratio (∆R) of four orders of magnitude. This photoconductivity rivals the best conductivity values described for though-transport conductive MOFs while maintaining a porosity of nearly 1.000 m2 ·g-1 . Submitted version https://hdl.handle.net/10481/101167 https://hdl.handle.net/10481/101166 A highly porous interpenetrated MOF-5-type network based on bipyrazolate linkers Quartapelle Procopio, Elsa; Muñoz Padial, Natalia; Masciocchi, Norberto; Galli, Simona; Oltra Ferrero, Juan Enrique; Barea, Elisa; Rodríguez Navarro, Jorge Andrés A novel cobalt(II) metal organic framework containing two interpenetrated nets with the cubic pcu-a topology of MOF-5 has been synthesized and characterized. In spite of being interpenetrated, this material exhibits a highly accessible porous structure. Published version https://hdl.handle.net/10481/101166 https://hdl.handle.net/10481/101165 Ti-Catalyzed straightforward synthesis of exocyclic allenes Muñoz Bascón, Juan; Hernandez Cervantes, Carmen; Muñoz Padial, Natalia; Álvarez Corral, Míriam; Rosales, Antonio; Rodríguez García, Ignacio; Oltra Ferrero, Juan Enrique Exocyclic allenes constitute useful building blocks in organic synthesis and have recently been identified as key intermediates in the synthesis of natural products. Here the first general method for the most straightforward synthesis of exocyclic allenes reported to date is presented. This method is based on the Barbier-type cyclization of propargyl halides catalyzed by titanium; a safe, abundant, and eco-friendly metal. The reaction proceeds under mild conditions compatible with different functional groups and provides good yields of five-, six-, and seven-membered carbocycles and nitrogen-containing heterocycles bearing an exocyclic allene group. Experimental evidence supporting the proposed reaction mechanism is also provided. Moreover, this procedure can be carried out in an enantioselective manner by using chiral titanocene(III) catalysts. The utility of this method has been proved in the synthesis of the natural alkaloid stemoamide. Published version https://hdl.handle.net/10481/101165 https://hdl.handle.net/10481/101163 Stereoselective Synthesis of Natural Products Promoted by Titanocene(III) M. Padial, Natalia; Roldan-Molina, Esther; Rosales, Antonio; Álvarez-Corral, Míriam; Rodríguez-García, Ignacio; Muñoz-Dorado, Manuel; Oltra, J. Enrique The use of radical reactions in organic synthesis is increasing every year. Bis(cyclopentadienil)titanium(III) chloride [Cp2TiCl] promotes and catalyzes several transformations under mild conditions compatible with several functional groups. Due to its power as a mild single-electron transfer reagent, Cp2TiCl has become a formidable tool in organic synthesis. Thus, this catalyst is being increasingly used in the synthesis of complex multifunctional molecules, mainly natural products and related compound useful in pharmacology. This chapter will include a comprehensive review of those works on Cp2TiCl-mediated synthesis of natural products published from 2006 onward, as there is a previous comprehensive review covering the subject until 2005. Published version https://hdl.handle.net/10481/101163