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Chiral metal–organic frameworks (MOFs) have gained rising attention as ordered nanoporous materials for enantiomer separations, chiral catalysis, and sensing. Among those, chiral MOFs are generally obtained through complex synthetic routes by using a limited choice of reactive chiral organic precursors as the primary linkers or auxiliary ligands. Here, we report a template‐controlled synthesis of chiral MOFs from achiral precursors grown on chiral nematic cellulose‐derived nanostructured bio‐templates. We demonstrate that chiral MOFs, specifically, zeolitic imidazolate framework (ZIF),unc‐[Zn(2‐MeIm)₂, 2‐MeIm=2‐methylimidazole], can be grown from regular precursors within nanoporous organized chiral nematic nanocellulosesviadirected assembly on twisted bundles of cellulose nanocrystals. The template‐grown chiral ZIF possesses tetragonal crystal structure with chiral space group ofP4₁, which is different from traditional cubic crystal structure ofI‐43 mfor freely grown conventional ZIF‐8. The uniaxially compressed dimensions of the unit cell of templated ZIF and crystalline dimensions are signatures of this structure. We observe that the templated chiral ZIF can facilitate the enantiotropic sensing. It shows enantioselective recognition and chiral sensing abilities with a low limit of detection of 39 μM and the corresponding limit of chiral detection of 300 μM for representative chiral amino acid, D‐ and L‐ alanine.

Chiral metal–organic frameworks (MOFs) have gained rising attention as ordered nanoporous materials for enantiomer separations, chiral catalysis, and sensing. Among those, chiral MOFs are generally obtained through complex synthetic routes by using a limited choice of reactive chiral organic precursors as the primary linkers or auxiliary ligands. Here, we report a template‐controlled synthesis of chiral MOFs from achiral precursors grown on chiral nematic cellulose‐derived nanostructured bio‐templates. We demonstrate that chiral MOFs, specifically, zeolitic imidazolate framework (ZIF),unc‐[Zn(2‐MeIm)₂, 2‐MeIm=2‐methylimidazole], can be grown from regular precursors within nanoporous organized chiral nematic nanocellulosesviadirected assembly on twisted bundles of cellulose nanocrystals. The template‐grown chiral ZIF possesses tetragonal crystal structure with chiral space group ofP4₁, which is different from traditional cubic crystal structure ofI‐43 mfor freely grown conventional ZIF‐8. The uniaxially compressed dimensions of the unit cell of templated ZIF and crystalline dimensions are signatures of this structure. We observe that the templated chiral ZIF can facilitate the enantiotropic sensing. It shows enantioselective recognition and chiral sensing abilities with a low limit of detection of 39 μM and the corresponding limit of chiral detection of 300 μM for representative chiral amino acid, D‐ and L‐ alanine.

Shape‐persistent, conductive ionogels where both mechanical strength and ionic conductivity are enhanced are developed using multiphase materials composed of cellulose nanocrystals and hyperbranched polymeric ionic liquids (PILs) as a mechanically strong supporting network matrix for ionic liquids with an interrupted ion‐conducting pathway. The integration of needlelike nanocrystals and PIL promotes the formation of multiple hydrogen bonding and electrostatic ionic interaction capacitance, resulting in the formation of interconnected networks capable of confining a high amount of ionic liquid (≈95 wt%) without losing its self‐sustained shape. The resulting nanoporous and robust ionogels possess outstanding mechanical strength with a high compressive elastic modulus (≈5.6 MPa), comparable to that of tough, rubbery materials. Surprisingly, these rigid materials preserve the high ionic conductivity of original ionic liquids (≈7.8 mS cm⁻¹), which are distributed within and supported by the nanocrystal network‐like rigid frame. On the one hand, such stable materials possess superior ionic conductivities in comparison to traditional solid electrolytes; on the other hand, the high compression resistance and shape‐persistence allow for easy handling in comparison to traditional fluidic electrolytes. The synergistic enhancement in ion transport and solid‐like mechanical properties afforded by these ionogel materials make them intriguing candidates for sustainable electrodeless energy storage and harvesting matrices.