Frontier Orbital Engineering of Metal–Organic Frameworks with Extended Inorganic Connectivity: Porous Alkaline-Earth Oxides

详细信息    查看全文

• 作者：Christopher H. Hendon ; Aron Walsh ; Mircea Dincă
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：August 1, 2016
• 年：2016
• 卷：55
• 期：15
• 页码：7265-7269
• 全文大小：372K
• 年卷期：0
• ISSN：1520-510X

文摘

The development of conductive metal–organic frameworks is challenging owing to poor electronic communication between metal clusters and the organic ligands that bridge them. One route to overcoming this bottleneck is to extend the inorganic dimensionality, while using the organic components to provide chemical functionality. Using density functional theory methods, we demonstrate how the properties of the alkaline-earth oxides SrO and BaO are transformed upon formation of porous solids with organic oxygen sources (acetate and trifluoroacetate). The electron affinity is significantly enhanced in the hybrid materials, while the ionization potential can be tuned over a large range with the polarity of the organic moiety. Furthermore, because of their high-vacuum fraction, these materials have dielectric properties suitable for low-κ applications.