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A flexible photoactive titanium metal-organic framework based on a [Ti-3(IV)(mu(3)-O)(O)(2)(COO)(6)] cluster

Bart Bueken, Frederik Vermoortele, Danny Vanpoucke (UGent) , Helge Reinsch, Chih-Chin Tsou, Pieterjan Valvekens, Trees De Baerdemaeker, Rob Ameloot, Christine EA Kirschhock, Veronique Van Speybroeck (UGent) , et al.
(2015) ANGEWANDTE CHEMIE-INTERNATIONAL EDITION. 54(47). p.13912-13917
Author
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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-cyclo-hexanedicarboxylate linkers and an unprecedented [Ti-3(IV)(mu(3)-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 Ti-IV center per cluster can be photoreduced to Ti-III 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.
Keywords
molecular modeling, photochemistry, metallocenes, metal-organic frameworks, titanium, EXTENDING HIRSHFELD-I, HETEROMETALLIC APPROACH, TITANOCENE DICHLORIDE, UNEXPECTED FORMATION, SORPTION PROPERTIES, PERIODIC MATERIALS, CRYSTAL-STRUCTURES, OXO CLUSTERS, SURFACE-AREA, HYDROLYSIS

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Chicago
Bueken, Bart, Frederik Vermoortele, Danny Vanpoucke, Helge Reinsch, Chih-Chin Tsou, Pieterjan Valvekens, Trees De Baerdemaeker, et al. 2015. “A Flexible Photoactive Titanium Metal-organic Framework Based on a [Ti-3(IV)(mu(3)-O)(O)(2)(COO)(6)] Cluster.” Angewandte Chemie-international Edition 54 (47): 13912–13917.
APA
Bueken, Bart, Vermoortele, F., Vanpoucke, D., Reinsch, H., Tsou, C.-C., Valvekens, P., De Baerdemaeker, T., et al. (2015). A flexible photoactive titanium metal-organic framework based on a [Ti-3(IV)(mu(3)-O)(O)(2)(COO)(6)] cluster. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 54(47), 13912–13917.
Vancouver
1.
Bueken B, Vermoortele F, Vanpoucke D, Reinsch H, Tsou C-C, Valvekens P, et al. A flexible photoactive titanium metal-organic framework based on a [Ti-3(IV)(mu(3)-O)(O)(2)(COO)(6)] cluster. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION. 2015;54(47):13912–7.
MLA
Bueken, Bart, Frederik Vermoortele, Danny Vanpoucke, et al. “A Flexible Photoactive Titanium Metal-organic Framework Based on a [Ti-3(IV)(mu(3)-O)(O)(2)(COO)(6)] Cluster.” ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 54.47 (2015): 13912–13917. Print.
@article{7061747,
  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-cyclo-hexanedicarboxylate linkers and an unprecedented [Ti-3(IV)(mu(3)-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 Ti-IV center per cluster can be photoreduced to Ti-III 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.},
  author       = {Bueken, Bart and Vermoortele, Frederik and Vanpoucke, Danny and Reinsch, Helge and Tsou, Chih-Chin and Valvekens, Pieterjan and De Baerdemaeker, Trees and Ameloot, Rob and Kirschhock, Christine EA and Van Speybroeck, Veronique and Mayer, James M and De Vos, Dirk},
  issn         = {1433-7851},
  journal      = {ANGEWANDTE CHEMIE-INTERNATIONAL EDITION},
  language     = {eng},
  number       = {47},
  pages        = {13912--13917},
  title        = {A flexible photoactive titanium metal-organic framework based on a [Ti-3(IV)(mu(3)-O)(O)(2)(COO)(6)] cluster},
  url          = {http://dx.doi.org/10.1002/anie.201505512},
  volume       = {54},
  year         = {2015},
}
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