Photochemical Synthesis, Properties and X‐Ray Crystal Structure of Tetrabutylammonium Dodecamolybdophosphate Heteropoly Blue

Abstract

AbstractThe title heteropoly blue, (Bu4N)6H10[PMo11VIMovO40]4 · H2O has been photochemically synthesized and characterized with elemental analysis, solid diffusion reflectance electronic spectra, CV, ESR, XFS, IR spectra, conductivity measurement and X‐ray single crystal analysis. The crystallographic data for C96H218Mo48N6O169P4 are as follows: Mr= 8889.76, triclinic, Pī, a = 1.4142 (3) nm, b = 2.6027 (5) nm, c = 2.6403 (5) nm, α= 113.96 (3)°, β = 90.05 (3)°, γ= 105.71 (3)°, V = 8.481 (3) nm3, Z = 1, Dc= 1.741 g/cm3, F (000) = 4264, μ = 1.798 mm−1. The X‐ray crystal structure analysis reveals that there is one independent molecule in the unit cell of the title heteropoly blue which contains four mixed‐valence heteropoly anions, six tetrabutylammonium cations and one water molecule. Its molecular structure possesses a centrosymmetrical arrangement in the unit cell. The phosphorus atom is in the crystallographic inversion center of the heteropoly anion and the eight oxygen atoms surrounding central phosphorus atom comprise of a distorted hexahedron. Heteropoly anion has two equal sets of PO4 tetrahedron. The PO4 tetrahedron and the MoO6 octahedron in the polyanion are greatly distorted.