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

The Royal Society of Chemistry Journal

Most developments in the chemistry and applications of metal–organic frameworks (MOFs) have been made possible thanks to the value of reticular chemistry in guiding the unlimited combination of organic connectors and secondary building units (SBUs) into targeted architectures. However, the development of new titanium-frameworks still remains limited by the difficulties in controlling the formation of persistent Ti-SBUs with predetermined directionality amenable to the isoreticular approach. Here we report the synthesis of a mesoporous Ti-MOF displaying a MIL-100 topology. MIL-100(Ti) combines excellent chemical stability and mesoporosity, intrinsic to this archetypical family of porous materials, with photoactive Ti3 (μ3-O) metal-oxo clusters. By using high-throughput synthetic methodologies, we have confirmed that the formation of this SBU is thermodynamically favored as it is not strictly dependent on the metal precursor of choice and can be regarded as an adequate building block to control the design of new Ti-MOF architectures. We are confident that the addition of a mesoporous solid to the small number of crystalline, porous titanium-frameworks available will be a valuable asset to accelerate the development of new porous photocatalysts without the pore size limitations currently imposed by the microporous materials available.

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

Javier Castells-Gil a, Natalia M. Padial ab, Neyvis Almora-Barrios a, Ivan da Silva c, Diego Mateo d, Josep Albero d, Hermenegildo García d and Carlos Martí-Gastaldo *a

a Universidad de Valencia (ICMol), Catedrático José Beltrán-2, 46980, Paterna, Spain

b Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA

c ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot, Oxfordshire OX11 0QX, UK

d Instituto Universitario de Tecnología Química CSIC-UPV, Universitat Politècnica de València, Av. De Los Naranjos s/n, 46022, Valencia, Spain

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The Royal Society of Chemistry 2019

DOI: 10.1039/C8SC05218B (Edge Article) Chem. Sci., 2019, 10, 4313-4321

For details please contact [email protected]

August 8, 2019