Matrix Isolation Studies of Group IV Oxides. II. Infrared Spectra and Structures of GeO, Ge2O2, Ge3O3, and Ge4O4

Abstract

The vapor‐phase germanium oxides GeO, Ge₂O₂, and Ge₃O₃ have been isolated in nitrogen and argon matrices. In a nitrogen matrix, infrared absorptions are observed at 973.4 (⁷⁴Ge¹⁶O); 667.0, 599.0 (Ge₂¹⁶O₂); 824, and 440 cm⁻¹ (Ge₃¹⁶O₃). A fourth species, Ge₄O₄, is formed on diffusion, and gives infrared absorptions at 553.3, 490.0, 476.0, and 457.5 cm⁻¹. With the aid of ¹⁸O substitution, estimates are obtained for the molecular dimensions of these species: Ge₂O₂ ($V_h$ symmetry), $r_{\mathrm{Ge–O}}\text{\hspace{0.17em}=\hspace{0.17em}1.87 Å, ∠}\mathrm{OGeO}\text{\hspace{0.17em}=\hspace{0.17em}83°;}{\mathrm{Ge}}_3{\mathrm{O}}_3$ ($D_{\text{3h}}$ symmetry), $R_{\mathrm{Ge–O}}\text{\hspace{0.17em}=\hspace{0.17em}1 85 Å, ∠}\mathrm{OGeO}\text{\hspace{0.17em}=\hspace{0.17em}100°}$ . The concentration changes occurring on diffusion are investigated.