Frontier Orbital Engineering of Metal-Organic Frameworks with Extended Inorganic Connectivity: Porous Alkaline-Earth Oxides.
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.
Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
Christopher H
CH
Hendon
Department of Chemistry, University of Bath , Bath BA2 7AY, U.K.|Global E3 Institute and Department of Materials Science and Engineering, Yonsei University , Seoul 120-749, Korea.
Aron
A
Walsh
Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
Mircea
M
Dincă