title: A Flexible Photoactive Titanium Metal-Organic Framework Based on a [Ti(IV)3(μ3-O)(O)2(COO)6] Cluster.
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 [Ti(IV)3(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 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.
authors.affiliation: Centre for Surface Chemistry and Catalysis, KU Leuven, Celestijnenlaan 200F, p.o. box 2461, 3001 Leuven (Belgium).
authors.forename: Bart
authors.initials: B
authors.lastname: Bueken
authors.affiliation: Centre for Surface Chemistry and Catalysis, KU Leuven, Celestijnenlaan 200F, p.o. box 2461, 3001 Leuven (Belgium).
authors.forename: Frederik
authors.initials: F
authors.lastname: Vermoortele
authors.affiliation: Center for Molecular Modeling, Ghent University, Technologiepark 903, 9052 Zwijnaarde (Belgium).
authors.forename: Danny E P
authors.initials: DE
authors.lastname: Vanpoucke
authors.affiliation: Centre for Surface Chemistry and Catalysis, KU Leuven, Celestijnenlaan 200F, p.o. box 2461, 3001 Leuven (Belgium).
authors.forename: Helge
authors.initials: H
authors.lastname: Reinsch
authors.affiliation: Department of Chemistry, Yale University, 225 Prospect Street, p.o. box 208107, New Haven, CT 06511 (USA).
authors.forename: Chih-Chin
authors.initials: CC
authors.lastname: Tsou
authors.affiliation: Centre for Surface Chemistry and Catalysis, KU Leuven, Celestijnenlaan 200F, p.o. box 2461, 3001 Leuven (Belgium).
authors.forename: Pieterjan
authors.initials: P
authors.lastname: Valvekens
authors.affiliation: Centre for Surface Chemistry and Catalysis, KU Leuven, Celestijnenlaan 200F, p.o. box 2461, 3001 Leuven (Belgium).
authors.forename: Trees
authors.initials: T
authors.lastname: De Baerdemaeker
authors.affiliation: Centre for Surface Chemistry and Catalysis, KU Leuven, Celestijnenlaan 200F, p.o. box 2461, 3001 Leuven (Belgium).
authors.forename: Rob
authors.initials: R
authors.lastname: Ameloot
authors.affiliation: Centre for Surface Chemistry and Catalysis, KU Leuven, Celestijnenlaan 200F, p.o. box 2461, 3001 Leuven (Belgium).
authors.forename: Christine E A
authors.initials: CE
authors.lastname: Kirschhock
authors.affiliation: Center for Molecular Modeling, Ghent University, Technologiepark 903, 9052 Zwijnaarde (Belgium).
authors.forename: Veronique
authors.initials: V
authors.lastname: Van Speybroeck
authors.affiliation: Department of Chemistry, Yale University, 225 Prospect Street, p.o. box 208107, New Haven, CT 06511 (USA).
authors.forename: James M
authors.initials: JM
authors.lastname: Mayer
authors.affiliation: Centre for Surface Chemistry and Catalysis, KU Leuven, Celestijnenlaan 200F, p.o. box 2461, 3001 Leuven (Belgium). dirk.devos@biw.kuleuven.be.
authors.forename: Dirk
authors.initials: D
authors.lastname: De Vos
keywords: metal-organic frameworks; metallocenes; molecular modeling; photochemistry; titanium