Engineering Crystal Symmetry and Polar Order in Molecular Host Frameworks

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Science  30 Nov 2001:
Vol. 294, Issue 5548, pp. 1907-1911
DOI: 10.1126/science.1064432

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A crystal design strategy is described that produces a series of solid-state molecular host frameworks with prescribed lattice metrics and polar crystallographic symmetries. This represents a significant advance in crystal engineering, which is typically limited to manipulation of only gross structural features. The host frameworks, constructed by connecting flexible hydrogen-bonded sheets with banana-shaped pillars, sustain one-dimensional channels that are occupied by guest molecules during crystallization. The polar host frameworks enforce the alignment of these guests into polar arrays, with properly chosen guests affording inclusion compounds that exhibit second harmonic generation because of this alignment. This protocol exemplifies a principal goal of modern organic solid-state chemistry: the precise control of crystal symmetry and structure for the attainment of a specific bulk property.

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