A Flexible Photoactive Titanium Metal-Organic Framework Based on a [Ti3IV(μ3-O)(O)2(COO)6] Cluster

被引：95

作者：

Bueken, Bart ^{[1
]}

Vermoortele, Frederik ^{[1
]}

Vanpoucke, Danny E. P. ^{[2
]}

Reinsch, Helge ^{[1
]}

Tsou, Chih-Chin ^{[3
]}

Valvekens, Pieterjan ^{[1
]}

De Baerdemaeker, Trees ^{[1
]}

Ameloot, Rob ^{[1
]}

Kirschhock, Christine E. A. ^{[1
]}

Van Speybroeck, Veronique ^{[2
]}

Mayer, James M. ^{[3
]}

De Vos, Dirk ^{[1
]}

机构：

[1] Katholieke Univ Leuven, Ctr Surface Chem & Catalysis, B-3001 Louvain, Belgium

[2] Univ Ghent, Ctr Mol Modeling, B-9052 Zwijnaarde, Belgium

[3] Yale Univ, Dept Chem, New Haven, CT 06511 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2015年 / 54卷 / 47期

基金：

美国国家科学基金会;

关键词：

metallocenes; metal-organic frameworks; molecular modeling; photochemistry; titanium; EXTENDING HIRSHFELD-I; UNEXPECTED FORMATION; SORPTION PROPERTIES; OXO CLUSTERS; HYDROLYSIS; TRINUCLEAR; COMPLEXES; CHEMISTRY; CATALYSTS; TOPOLOGY;

D O I：

10.1002/anie.201505512

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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.

引用

页码：13912 / 13917

页数：6

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