New structural units in molybdenum oxyfluoride chemistry

Abstract

The solvothermal syntheses and crystal structures of five new molybdenum oxyfluorides are presented. ). Mo-Mo bonding is observed in each of the new building units. KeywordsMolybdenum oxyfluoride; solvothermal synthesis; metal-metal bonding; crystal structure Highlights  A facile route to novel reduced molybdenum oxyfluorides  New dimer and tetramer units containing Mo-Mo bonds  First example of a reduced, infinitely extended molybdenum oxyfluoride

Lewis Acidic Behavior of MoOF4 towards the Alkali Metal Fluorides in Anhydrous Hydrogen Fluoride Solutions

“…[16] However, since the samples presented in this work were handled under strictly-dried atmospheres, and because there is no evidence of water or hydroxides in the spectra presented here, it seems highly unlikely that the bands observed in this work arise because of hydrolysis products. Moreover, in the work of Bougon 5 ] but gave no further discussion on the occurrence of the remaining bands. [12] To determine if the [MoOF 5 ]anion is responsible for the observation of bands arising between 850 and 990 cm -1 in the spectra reported here, an IR spectrum of a C 4v [MoOF 5 ]anion was calculated using the DFT-PBE0 density functional method and the def2-TZVP basis set ( Figure S19, Table S9).…”

“…[40,41] A triple-zeta-valence + polarization (TZVP) level basis set was applied for Mo and splitvalence + polarization (SVP) level basis sets were applied for the other atoms. The basis set for Mo was taken from a previous study on MoF 5 . [27] The basis sets for Li, Na, K, Rb, Cs, O, and F were also taken from previous studies (see Supporting Information for full basis set details).…”

“…The harmonic vibrational frequencies, IR intensities, and Raman intensities were obtained by using the computational scheme implemented in CRYSTAL17 [5][6][7][8]. [47][48][49][50] The Raman intensities were calculated for a polycrystalline powder sample (total isotropic intensity in arbitrary units).…”

“…This distortion, characterized by a displacement of the Mo atom from the center of its octahedral coordination environment, and alternating atomic distances between the Mo and neighboring bridging fluorine/oxygen atoms, can yield compounds displaying metallic, ferroelectric, and magnetic behaviors . In order to exploit potential promising physical and chemical properties, many molybdenum oxide fluorides have been synthesized to date . However, little remains known regarding the chemical properties of the simplest Mo VI molybdenum oxide fluoride, MoOF 4 .…”

“…[3] In order to exploit potential promising physical and chemical properties, many molybdenum oxide fluorides have been synthesized to date. [4][5][6][7][8] However, little remains known regarding the chemical properties of the simplest Mo VI molybdenum oxide fluoride, MoOF 4 .…”