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

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• 作者：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
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：August 1, 2016
• 年：2016
• 卷：55
• 期：15
• 页码：7192-7199
• 全文大小：563K
• 年卷期：0
• ISSN：1520-510X

文摘

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.