Chemistry

Metal-Free Perovskites

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Science  13 Sep 2002:
Vol. 297, Issue 5588, pp. 1771
DOI: 10.1126/science.297.5588.1771a

Molecular analogs of perovskites, which includes important mantle minerals and high-temperature superconductors, have been synthesized. Bremner et al. crystallized cubic and 2-H hexagonal variants of a perovskite in which (NH4)Cl6 octahedra form the building blocks of a corner-sharing network. In the cubic form, the cation is the doubly hydrated piperazinium cation C4N2H122+, which occupies its site along with a water molecule that helps create a stabilizing hydrogen-bonding network not seen in inorganic perovskites. The hexagonal variant, whose prototype is BaNiO3, is formed by the larger doubly protonated Dabconium cation C6N2H142+ and is also stabilized by hydrogen bonds. The ease of synthesis suggests that it should be possible to create optically active noncentrosymmetric as well as chiral analogs by using other templating cations. — PDS

J. Am. Chem. Soc. 10.1021/ja027484e (2002).

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