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

Hala Assi; Laura C. Pardo Pérez; Georges Mouchaham; Florence Ragon; Maxim Nasalevich; Nathalie Guillou; Charlotte Martineau; Hubert Chevreau; Freek Kapteijn; Jorge Gascon; Pierre Fertey; Erik Elkaim; Christian Serre; Thomas Devic

doi:10.1021/acs.inorgchem.6b01060

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

Hala Assi, Laura C. Pardo Pérez, Georges Mouchaham, Florence Ragon, Maxim Nasalevich, Nathalie Guillou, Charlotte Martineau, Hubert Chevreau, Freek Kapteijn, Jorge Gascon, Pierre Fertey, Erik Elkaim, Christian Serre^*, Thomas Devic

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

74 Scopus citations

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.

Original language	English (US)
Pages (from-to)	7192-7199
Number of pages	8
Journal	Inorganic chemistry
Volume	55
Issue number	15
DOIs	https://doi.org/10.1021/acs.inorgchem.6b01060
State	Published - Aug 1 2016

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Publisher Copyright:
© 2016 American Chemical Society.

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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Assi, H., Pardo Pérez, L. C., Mouchaham, G., Ragon, F., Nasalevich, M., Guillou, N., Martineau, C., Chevreau, H., Kapteijn, F., Gascon, J., Fertey, P., Elkaim, E., Serre, C., & Devic, T. (2016). Investigating the Case of Titanium(IV) Carboxyphenolate Photoactive Coordination Polymers. Inorganic chemistry, 55(15), 7192-7199. 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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doi = "10.1021/acs.inorgchem.6b01060",

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AU - Nasalevich, Maxim

AU - Guillou, Nathalie

AU - Martineau, Charlotte

AU - Chevreau, Hubert

AU - Kapteijn, Freek

AU - Gascon, Jorge

AU - Fertey, Pierre

AU - Elkaim, Erik

AU - Serre, Christian

AU - Devic, Thomas

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

Abstract

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