期刊
CRYSTAL GROWTH & DESIGN
卷 11, 期 12, 页码 5200-5205出版社
AMER CHEMICAL SOC
DOI: 10.1021/cg201299n
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A slow liquid-gas diffusion method in strong acid conditions has allowed stabilizing for the first time in the solid state the diprotonated form of the 4,4'-bipyridine-N,N'-dioxide (bp4do), H(2)bp4do(2+) as two polymophs of the chloride salt (H(2)bp4do)Cl-2, while in the presence of a metallic salt M((III))Br-3 (M = Bi, Sb), the monoprotonated form Hbp4do(+) is mainly stabilized as (Hbp4do)(2)[Sb2Br8] and (H(2)bp4do)(Hbp4do)(4-)[Bi4Br18]center dot 2H(2)O. The dehydration of this last phase leads to (H(2)bp4do)(Hbp4do)(4)[Bi4Br18]. In the structures of (H(2)bp4do)Cl-2 salts, the hydroxyl H atoms point toward the chloride anions leading to close (O)H center dot center dot center dot Cl contacts in the range 1.831-1.839 angstrom. A one-dimensional network of H-bonded Hbp4do(+) cations is found in the structure of (Hbp4do)(2)[Sb2Br8], whereas H-bonded supramolecular cations of five entities are found in the structures of bromobismuthate salts. In all the halometallate structures, X-ray analyses (293 K and 120 K data) did not allow us to locate the acid H atoms of protonated bp4do molecules certainly due to a disorder phenomenon but also revealing an asymmetrical H-bonding situation. The bromobismuthate hybrids are nonlinear optical active with a powder second harmonic generation efficiency being half that of urea.
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