Growing Molecular Crystals on Inorganic Crystals: Polar Structure Induced by Noncentrosymmetric Templates

Abstract

Like promotes like: The templating effect of inorganic crystals is exploited to promote the growth of the polar structure of a molecular crystal of a dipolar zinc(II) complex (see picture). It is likely that the polar nature of the noncentrosymmetric template crystal lattice, and its associated electrostatic field, facilitates the oriented assembly of the dipolar molecules.

Recent Advances in the Asymmetric Growth of Organic Polar Crystals: A Review

“…Examples of templates and additives in the regulation of organic polar crystal nucleation and growth. (a) Molecular structure of ZNPPA and a schematic representation of the molecular assembly of the dimorphic structures 1 and 2 . (b, c) SEM images showing ZNPPA crystals growing on K 2 SO 4 and NaBrO 3 template crystals .…”

“…As a result, when nucleation occurs, the system will spontaneously adapt to the organic–inorganic interface for maximum matching to exert an intervention in the kinetics, thereby ensuring well-controlled nucleation and growth . As for the organic polar crystals, where molecules are more inclined to form centrosymmetric structures (Figure a), Prakash had developed a method to induce polar structures of (4-pyrrolidinopyr-idyl)­bis­(acetylacetonato)­zinc­(II) (ZAPPA) using noncentrosymmetric templates. As shown in Figure b,c, ZNPPA 1 has a cuboid and ZNPPA 2 has a truncated pyramid shape with the SHG.…”

“…(a) Molecular structure of ZNPPA and a schematic representation of the molecular assembly of the dimorphic structures 1 and 2 . (b, c) SEM images showing ZNPPA crystals growing on K 2 SO 4 and NaBrO 3 template crystals . (d) Illustration of l -alanine and l -glutamic acid as stereoselective habit modification of α-glycine crystals .…”

Structure-Directing Self-Assembly, Structures and Characterization of Four d0-Transition Metal Oxide/Fluoride Compounds Constructed with Imidazole/1-Methylimidazole/1-Vinylimidazole and Copper(II)/Zinc(II)

“…The rational design of crystal structures based on the chemical nature of molecular components is an exciting research topic, and an emerging theme of crystal engineering in inorganic solid state chemistry. − In particular, the solid structures with different dimensionality (three-dimensional (3D), two-dimensional (2D), one-dimensional (1D), and zero-dimensional (0D)) are very important for exhibiting diversities of physical and chemical properties. − …”

Two New Nonlinear Optical and Ferroelectric Three-Dimensional Metal−Organic Frameworks with an sqp-net

“…The rational synthesis and design of noncentrosymmetric or polar compounds have attracted considerable attention in functional materials with specific chemical and physical properties such as nonlinear optical (NLO) second harmonic generation (SHG), piezoelectricity, pyroelectricity, and ferroelectricity. − Of particular importance are nonlinear SHG and ferroelectricity, because the former plays an important role in telecommunications, optical storage, and information processing, and the latter may be useful in some scientific fields such as switchable NLO devices, ferroelectric random access memories, and light modulators . Up to now, there are some documents of SHG response and ferroelectricity in pure organic or inorganic compounds; however, investigation of metal−organic frameworks (MOFs) possessing NLO-active and ferroelecitric behaviors remains relatively scarce. ,, …”