Structural diversities induced by cation sizes in a series of fluorogermanophosphates: A[GeF(HPO)] (A = Na, K, Rb, NH, and Cs).

Germanophosphates, in comparison with other metal phosphates, have been less studied but potentially exhibit more diverse structural chemistry with wide applications. Herein we applied a hydro-/solvo-fluorothermal route to make use of both the "tailor effect" of fluoride for the formation of low dimensional anionic clusters and the presence of alkali cations of different sizes to align the anionic clusters to control the overall crystal symmetries of germanophosphates. The synergetic effects of fluoride and alkali cations led to structural changes from chain-like structures to layered structures in a series of five novel fluorogermanophosphates: A[GeF(HPO)] (A = Na, K, Rb, NH, and Cs, denoted as Na, K, Rb, NH4, and Cs).