Physical Chemistry Chemical Physics Properties of Irmof-14 and Its Analogues M-irmof-14 (m = Cd, Alkaline Earth Metals): Electronic Structure, Structural Stability, Chemical Bonding, and Optical Propertiesw

COVER ARTICLE Katayama et al. Reaction kinetics of dye decomposition processes monitored inside a photocatalytic microreactor HOT ARTICLE Yu et al. Reconstruction of the (001) surface of TiO 2 nanosheets induced by the fl uorine-surfactant removal process under UV-irradiation for dye-sensitized solar cells The chemical bonding, electronic structure, and optical properties of the experimentally available metal–organic framework IRMOF-14 and its metal-substituted analogues M-IRMOF-14 systematically investigated using DFT calculations. The unit cell volume and atomic positions were optimized with the Perdew–Burke–Ernzerhof (PBE) functional and showed good agreement between experimental and theoretical equilibrium structural parameters for Zn-IRMOF-14. The calculated bulk moduli indicate that the whole M-IRMOF-14 series are soft materials. The estimated band gap from DOS calculations for the M-IRMOF-14 series is ca. 2.5 eV, essentially independent of the metal ion and indicative of nonmetallic character. The band gap value is distinctly different from those calculated previously for the M-IRMOF-1 (benzene-1,4-dicarboxylate linker; ca. 3.5 eV) and M-IRMOF-10 (biphenyl-4,4 0-dicarboxylate linker; ca. 3.0 eV) series and this confirms that the identity of the linker is a key parameter to control band gaps in an isoreticular series of main-group MOFs. In view of potential uses of MOFs in organic semiconducting devices such as field-effect transistors, solar cells, and organic light-emitting devices, the linear optical properties of these materials were also investigated. Comparisons are made with the M-IRMOF-1 and M-IRMOF-10 series.