Abstract
The coexistence of single-crystallinity with a multidomain morphology is a paradoxical phenomenon occurring in biomineralization. Translating such feature to synthetic materials is a highly challenging process in crystal engineering. We demonstrate the formation of metallo-organic single-crystals with a unique appearance: six-connected half-rods forming a hexagonal-like tube. These uniform objects are formed from unstable, monodomain crystals. The monodomain crystals dissolve from the inner regions, while material is anisotropically added to their shell, resulting in hollow, single-crystals. Regardless of the different morphologies and growth mechanism, the crystallographic structures of the mono- and multidomain crystals are nearly identical. The chiral crystals are formed from achiral components, and belong to a rare space group (P622). Sonication of the solvents generating radical species is essential for forming the multidomain single-crystals. This process reduces the concentration of the active metal salt. Our approach offers opportunities to generate a new class of crystals.
Highlights
The coexistence of single-crystallinity with a multidomain morphology is a paradoxical phenomenon occurring in biomineralization
Unlike bio-crystallization, where crystal shaping is under cellular control, mastering of crystallization chemistry and kinetics is required for synthetic materials
The solution containing the Tetrakis{4[(E)-2-pyridin-4-yl-vinyl]phenyl} adamantane (TPVA) was mixed with a DMF solution of the metal salt in a glass pressure tube and heated at 105 °C for 48 h, resulting in the formation of a green precipitate (Fig. 1a)
Summary
The coexistence of single-crystallinity with a multidomain morphology is a paradoxical phenomenon occurring in biomineralization. Several works have shown that control over crystal size and shape can affect porosity[21], catalytic activity[22], and cellular uptake[23], to date, the majority of the efforts have been aimed at designing the crystal structures of MOFs24 This fact has confined much of the ongoing research to applications that exploit the porosity of the molecular frameworks[25,26]. Our group has recently shown that a variability of uniform metallo-organic crystals with different morphologies can be obtained[28,29,30] These studies include the formation of a unique yoyo-shaped, single crystal exhibiting both a multidomain and chiral morphology[30]. The multidomain crystals have curved morphological features and retain single-crystallinity
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