A Flexible Photoactive Titanium Metal–Organic Framework Based on a [TiIV3(μ3‐O)(O)2(COO)6] Cluster. (25th September 2015)

• Record Type: Journal Article
• Authors: Bueken, Bart; Vermoortele, Frederik; Vanpoucke, Danny E. P.; Reinsch, Helge; Tsou, Chih‐Chin; Valvekens, Pieterjan; De Baerdemaeker, Trees; Ameloot, Rob; Kirschhock, Christine E. A.; Van Speybroeck, Veronique; Mayer, James M.; De Vos, Dirk
• Is Part Of: Angewandte Chemie. Volume 127:Number 47(2015)
• Page Start: 14118
• Page End: 14123
• Publication Date: 2015-09-25
• Subjects: Metallocene -- Metall‐organische Gerüstverbindungen -- Molecular Modeling -- Photochemie -- Titan; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201505512
• Languages: English
• ISSNs: 0044-8249

Abstract

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. Abstract : Atmungsaktiv : Titanocendichlorid dient als Metallquelle in einem innovativen Syntheseansatz für Metall‐organische Gerüstverbindungen (MOFs). Damit wurde ein „atmendes"︁ Ti‐MOF (COK‐69), das einen photoaktiven dreikernigen Cluster enthält, aus trans ‐1, 4‐Cyclohexandicarboxylat und einem ungewöhnlichen, photoaktiven anorganischen [Ti IV 3 (μ3 ‐O)(COO)6 ]‐Baustein aufgebaut (siehe Bild).