A Flexible Photoactive Titanium Metal–Organic Framework Based on a [TiIV3(μ3‐O)(O)2(COO)6] Cluster |
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| Authors: | Bart Bueken Dr Frederik Vermoortele Dr Danny E P Vanpoucke Dr Helge Reinsch Dr Chih‐Chin Tsou Dr Pieterjan Valvekens Dr Trees De?Baerdemaeker Prof?Dr Rob Ameloot Prof?Dr Christine E A Kirschhock Prof?Dr Veronique Van?Speybroeck Prof?Dr James M Mayer Prof?Dr Dirk De?Vos |
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| Affiliation: | 1. Centre for Surface Chemistry and Catalysis, KU Leuven, Celestijnenlaan 200F, p.o. box 2461, 3001 Leuven (Belgium);2. Center for Molecular Modeling, Ghent University, Technologiepark 903, 9052 Zwijnaarde (Belgium);3. Department of Chemistry, Yale University, 225 Prospect Street, p.o. box 208107, New Haven, CT 06511 (USA) |
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| Abstract: | The synthesis of titanium–carboxylate metal–organic frameworks (MOFs) is hampered by the high reactivity of the commonly employed alkoxide precursors. Herein, we present an innovative approach to titanium‐based MOFs by the use of titanocene dichloride to synthesize COK‐69, the first breathing Ti MOF, which is built up from trans‐1,4‐cyclohexanedicarboxylate linkers and an unprecedented TiIV3(μ3‐O)(O)2(COO)6] cluster. The photoactive properties of COK‐69 were investigated in depth by proton‐coupled electron‐transfer experiments, which revealed that up to one TiIV center per cluster can be photoreduced to TiIII while preserving the structural integrity of the framework. The electronic structure of COK‐69 was determined by molecular modeling, and a band gap of 3.77 eV was found. |
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| Keywords: | metallocenes metal– organic frameworks molecular modeling photochemistry titanium |
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