Chemistry of Metal Silicates and Germanates: The Largest Metal Polygermanate, K₁₁Mn₂₁Ge₃₂O₈₆(OH)₉(H₂O), with a 76 Å Periodic Lattice

Abstract

An examination of manganese silicates and germanates revealed unusual structural motifs and extremely different chemistries, with identical hydrothermal reactions forming K 2 Mn 2 Si 3 O 9 versus K 11 Mn 21 Ge 32 O 86 (OH) 9 (H 2 O). The germanate is exceptional in both its c-axis length (exceeding 76 Å) and unit cell volume (nearly 18000 Å 3 ), the largest known polygermanate structure to our knowledge.

Hydrothermal Synthesis and Crystal Structure of Vesuvianite Compounds, Ca19Al13Si18O71(OH)7 and Sr19Fe12Ge19O72(OH)6

“…We were also curious if the vesuvianite structure type could be expanded into a new phase space through the substitution of the larger tetrahedral Ge 4+ ion for Si 4+ . We have recently been examining the role of germanate as a building block in transition metal oxides and have observed some complex structural chemistry [23,24]. In the present case, we found that the larger germanate can accommodate the larger Fe 3+ ion in the trivalent Al 3+ sites, as well as the larger Sr 2+ ion in the Ca 2+ sites.…”

Sawtooth chains self-assembled from clusters of MnO6 octahedra within the silicate framework of K3Mn4Si10O24.33(H2O,OH)3/V,B

“…The specific heat reaches approximately 600 J mol −1 K −1 near room temperature which is significantly less than 3 Rn . Thus, the Debye temperature here exceeds 300 K, and the upper limit for lattice contribution C lat = βT , 3 β = 1943.7 n / Θ D , 3 can be estimated to be 0.3 J mol −1 K −1 or less than 5% at 5 K.…”

“…Innovative crystalline compounds have a significant role as the basis of future functional resources. [1][2][3][4] Silicates, the widespread minerals in the earth's crust, are among the most promising objects for experimental modeling of their nature-friendly synthetic archetypes. In particular, manganese silicates represent very attractive compounds because of the low cost and high availability of Mn, which is the eighth most abundant metal in the earth's crust.…”

Detection of Ge-Containing Adlayers at the Liquid Hg/Water Interface by In Situ X-ray Reflectivity in Aqueous Borate Electrolytes Containing Dissolved GeO2

“…Polygermanates are a class of macromolecular germanium oxyanions composed of edge-sharing GeO 6 octahedra and GeO 4 tetrahedra. − These oxyanions can exhibit a variety of sizes and structures, i.e., from linear chains to porous networks. , In the solid state, polygermanates are charge-stabilized by small cations. If the positive surface charge at an electrode surface, kept at potentials positive of E pzc , similarly stabilizes polygermanate anions, polygermanates may be the relevant species indicated by the XRR data.…”