Details

Autor(en) / Beteiligte

• Yang, Li-Ming
• Ravindran, Ponniah
• Vajeeston, Ponniah
• Tilset, Mats

Titel

Properties of IRMOF-14 and its analogues M-IRMOF-14 (M = Cd, alkaline earth metals): electronic structure, structural stability, chemical bonding, and optical propertiesElectronic supplementary information (ESI) available: Calculated charge density, charge transfer, and electron localization function (ELF) plots, total density of states (TDOS) and partial density of states (PDOS), band structures and optical properties of M-IRMOF-14 (M = Cd, Be, Mg, Ca, Sr and Ba). See DOI: 10.1039/c2cp24091b

Erscheinungsjahr

2012-03

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The chemical bonding, electronic structure, and optical properties of the experimentally available metalorganic framework IRMOF-14 and its metal-substituted analogues M-IRMOF-14 (M = Zn, Cd, Be, Mg, Ca, Sr, Ba), which contain a pyrene-2,7-dicarboxylate linker group, have been systematically investigated using DFT calculations. The unit cell volume and atomic positions were optimized with the PerdewBurkeErnzerhof (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-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. DFT studies of M-IRMOF-14 (M = Zn, Cd, Be, Mg, Ca, Sr, Ba) reveal that the 2.5 eV bandgap is independent of M and smaller than what has been seen in the M-IRMOF-1 and M-IRMOF-10 analogues by 1.0 and 0.5 eV, respectively.