TY - JOUR
T1 - Crystalline Ammonium Peroxogermanate as a Waste-Free, Fully Recyclable Versatile Precursor for Germanium Compounds
AU - Grishanov, Dmitry A.
AU - Churakov, Andrei V.
AU - Medvedev, Alexander G.
AU - Mikhaylov, Alexey A.
AU - Lev, Ovadia
AU - Prikhodchenko, Petr V.
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/2/4
Y1 - 2019/2/4
N2 - High, nearly 100%, yield synthesis of ammonium peroxogermanate (APG), (NH4)6[Ge6(μ-OO)6(μ-O)6(OH)6]·6H2O, is presented, and its crystal structure is determined by single crystal X-ray study. It comprises centrosymmetric hexanuclear peroxogermanate anions [Ge6(μ-OO)6(μ-O)6(OH)6]6- with six μ-oxo- and six μ-peroxo groups forming negatively charged layers. The space between these layers is filled by ammonium cations and water molecules, forming a highly stable structure due to hydrogen bonding. Highly soluble macroporous amorphous germanium oxide (HSGO) is then synthesized by mild treatment of APG. The compound forms highly oversaturated metastable germanium oxide solution with a solubility of 100 g/L, over 20 times higher than the solubility of amorphous germanium oxide. HSGO solution is a versatile reagent that can react with basic and acidic reagents to give a diverse range of salts including, e.g., germanium sulfide, germanium hydrophosphate, and potassium germanate. In the absence of acid or base, the aqueous HSGO solution yields hexagonal germanium oxide under ambient conditions.
AB - High, nearly 100%, yield synthesis of ammonium peroxogermanate (APG), (NH4)6[Ge6(μ-OO)6(μ-O)6(OH)6]·6H2O, is presented, and its crystal structure is determined by single crystal X-ray study. It comprises centrosymmetric hexanuclear peroxogermanate anions [Ge6(μ-OO)6(μ-O)6(OH)6]6- with six μ-oxo- and six μ-peroxo groups forming negatively charged layers. The space between these layers is filled by ammonium cations and water molecules, forming a highly stable structure due to hydrogen bonding. Highly soluble macroporous amorphous germanium oxide (HSGO) is then synthesized by mild treatment of APG. The compound forms highly oversaturated metastable germanium oxide solution with a solubility of 100 g/L, over 20 times higher than the solubility of amorphous germanium oxide. HSGO solution is a versatile reagent that can react with basic and acidic reagents to give a diverse range of salts including, e.g., germanium sulfide, germanium hydrophosphate, and potassium germanate. In the absence of acid or base, the aqueous HSGO solution yields hexagonal germanium oxide under ambient conditions.
UR - http://www.scopus.com/inward/record.url?scp=85060206144&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.8b02747
DO - 10.1021/acs.inorgchem.8b02747
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C2 - 30649865
AN - SCOPUS:85060206144
SN - 0020-1669
VL - 58
SP - 1905
EP - 1911
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 3
ER -