Inorganic Polar Blocks into Controlled Acentric Assemblies

We show here a strategy to predict the crystal structure,
formulate,
and prepare new noncentrosymmetric (NCS) bismuth–phosphate
based compounds. It is based on the cooperative-arrangement of polar
building units (BUs) which can be created at particular stoichiometric
conditions. The arrangement of such BUs into NCS compounds arise from
the shortest-periodicity of repartition of the cationic charges in
NCS structures than in the plausible, but never observed centrosymetric
polytypes. This work validates the possibilities for the prediction
of an extended series of novel compounds, tuning the size of BUs within
a variety of controlled edifices. Despite their closed chemical composition,
all the predicted terms appeared strikingly stable at precise stoichiometries.