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Publications in Scientific Journals:

M. Weil, M. Puchberger, E. Füglein, E. J. Baran, J. Vannahme, H. Jakobsen:
"Single-Crystal Growth and Characterization of Disilver(I) Monofluorophosphate(V), Ag2PO3F: Crystal Structure, Thermal Behavior, Vibrational Spectroscopy, and Solid-State 19F, 31P, and 109Ag MAS NMR Spectroscopy";
Inorganic Chemistry, 46 (2007), 801 - 808.



English abstract:
Single crystals of disilver(I) monofluorophosphate(V), Ag2PO3F (1), were obtained by slow evaporation of a diluted aqueous Ag2PO3F solution. Compound 1 adopts a new structure type and crystallizes in the monoclinic space group C2/c with eight formula units and lattice parameters of a) 9.2456(8) Å, b) 5.5854(5) Å, c) 14.7840(13) Å, and β = 90.178(2)°. The crystal structure of 1 [R(F2) > 2σ(F2) 0.0268, wR(F2 all) 0.0665] is composed of three crystallographically independent Ag+ cations and PO3F2- anions as single building units. The oxygen environment around each of the Ag+ cations is different, with one Ag+ in distorted octahedral (d (Ag-O) ) 2.553 Å), one in nearly rectangular (d (Ag-O) ) 2.445 Å), and one in distorted tetrahedral (d (Ag-O) ) 2.399 Å) coordination.
Additional Ag-F contacts to more remote F atoms located at distances >2.80 Å augment the coordination polyhedra for the two latter Ag+ cations. The monofluorophosphate anion deviates slightly from C3v symmetry and exhibits the characteristic differences in bond lengths, with a mean of 1.510 Å for the P-O bonds and one considerably longer P-F bond of 1.575(2) Å. Compound 1 was further characterized by vibrational spectroscopy (Raman and IR) and solid-state 19F, 31P, and 109Ag MAS NMR spectroscopy. The value for the isotropic one-bond P-F coupling constant in 1 is 1JPF = 1045 Hz. Thermal analysis (TG, DSC) revealed a reversible phase transition at 308 °C, which is very close to the decomposition range of 1. Under release of POF3, Ag4 P2O7 and Ag3PO4 are the thermal decomposition products at temperatures above 450 °C.

Created from the Publication Database of the Vienna University of Technology.