Much shorter hydrogen bonds with unexpected directional properties are formed by Ñuoride ligands in comparison to their heavier halogen congeners (X = Cl, Br, I). Ab initio calculations elucidate the underlying electronic origin of this geometric behavior. The viability of hydrogen bonding is clearly established for all donor-acceptor combinations, D-HAE AE AEX-M (D = C, N, O ; X = F, Cl, Br, I).
A synthetic strategy for constructing ionic hydrogen-bonded materials by combining perhalometallate anions with cations able to serve as hydrogen bond donors is presented. The approach is based on identification of well defined hydrogen bond acceptor sites on the anions by a combination of experimental and theoretical approaches. Selective population of these sites by hydrogen bond donors has the potential to afford organized crystalline arrays in one, two, or three dimensions. The approach is applicable to a wide range of metal centers.
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