Investigating the Case of Titanium(IV) Carboxyphenolate Photoactive Coordination Polymers

Journal Article (2016)
Authors

Hala Assi (ChemE/Catalysis Engineering, Université Paris-Saclay)

Laura C. Pardo Pérez (Université Paris-Saclay)

Georges Mouchaham (Université Paris-Saclay)

Florence Ragon (Université Paris-Saclay)

M Nasalevich (ChemE/Catalysis Engineering)

Nathalie Guillou (Université Paris-Saclay)

Charlotte Martineau (University Paris-Saclay, Université d'Orléans)

Hubert Chevreau (Université Paris-Saclay)

F. Kapteijn (ChemE/Catalysis Engineering)

Jorge Gascon Sabate (ChemE/Catalysis Engineering)

Pierre Fertey (L'Orme les Merisiers Saint-Aubin)

Erik Elkaim (L'Orme les Merisiers Saint-Aubin)

Christian Serre (Université Paris-Saclay)

Thomas Devic (Université Paris-Saclay)

Affiliation
ChemE/Catalysis Engineering
Copyright
© 2016 H. Assi, Laura C. Pardo Pérez, Georges Mouchaham, Florence Ragon, M. Nasalevich, Nathalie Guillou, Charlotte Martineau, Hubert Chevreau, F. Kapteijn, Jorge Gascon, Pierre Fertey, Erik Elkaim, Christian Serre, Thomas Devic
To reference this document use:
https://doi.org/10.1021/acs.inorgchem.6b01060
More Info
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Publication Year
2016
Language
English
Copyright
© 2016 H. Assi, Laura C. Pardo Pérez, Georges Mouchaham, Florence Ragon, M. Nasalevich, Nathalie Guillou, Charlotte Martineau, Hubert Chevreau, F. Kapteijn, Jorge Gascon, Pierre Fertey, Erik Elkaim, Christian Serre, Thomas Devic
Affiliation
ChemE/Catalysis Engineering
Bibliographical Note
Accepted Author Manuscript@en
Issue number
15
Volume number
55
Pages (from-to)
7192-7199
DOI:
https://doi.org/10.1021/acs.inorgchem.6b01060
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Abstract

The reactivity of 2,5-dihydroxyterephthalic acid (H4DOBDC) with titanium(IV) precursors was thoroughly investigated for the synthesis of metal-organic frameworks under solvothermal conditions. Four crystalline phases were isolated whose structures were studied by a combination of single-crystal or powder X-ray diffraction and solid-state NMR. The strong coordination ability of the phenolate moieties was found to favor the formation of isolated TiO6 octahedra bearing solely organic ligands in the resulting structures, unless hydrothermal conditions and precondensed inorganic precursors are used. It is worth noting that these solids strongly absorb visible light, as a consequence of the ligand-to-metal charge transfer (LMCT) arising from Ti-phenolate bonds. Preliminary photocatalytic tests suggest that one compound, namely, MIL-167, presents a higher activity for hydrogen evolution than the titanium carboxylate MIL-125-NH2 but that such an effect cannot be directly correlated with its improved light absorption feature.

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