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<p>Chiral metal-organic frameworks (CMOFs) are promising materials for catalysis, chromatography, and sensor applications. Typically, chirality in such frameworks is achieved by using chiral ligands. However, there are rare examples of CMOFs that form without any chiral source, usually via spontaneous symmetry breaking, resulting in supramolecular chirality. Germanium oxide framework SU-MB exhibits a unique mechanism of chirality emergence: during synthesis, only micropores of one handedness are selectively filled. This paper investigates the adsorption of limonene and α-pinene enantiomers on SU-MB. The framework demonstrated consistent enantioselectivity for both pairs of enantiomers, with a higher selectivity coefficient observed for α-pinenes than for limonenes. This difference arises from distinct trends in the isosteric heats of adsorption (Q<sub>st</sub>): for limonenes and (−)-α-pinene, Q<sub>st</sub> approaches the heat of liquefaction with increasing adsorption, whereas for (+)-α-pinene, Q<sub>st</sub> remains unchanged. These findings show that even a non-chiral crystal without chiral centers can exhibit enantioselectivity in adsorption processes, because of helical pores of one handedness.</p>

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Enantioselective adsorption of limonenes and α-pinenes on germanium oxide metal-organic framework

  • 期刊论文

  • 发表日期：

    2026年2月20日

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  • Yulia Sharafutdinova,
  • Klavdia Sufiyarova,
  • Adelina Samarina,
  • Diana Bagdanova,
  • Marat Agliullin,
  • Timur Mukhametzyanov,
  • Vladimir Guskov

摘要

Chiral metal-organic frameworks (CMOFs) are promising materials for catalysis, chromatography, and sensor applications. Typically, chirality in such frameworks is achieved by using chiral ligands. However, there are rare examples of CMOFs that form without any chiral source, usually via spontaneous symmetry breaking, resulting in supramolecular chirality. Germanium oxide framework SU-MB exhibits a unique mechanism of chirality emergence: during synthesis, only micropores of one handedness are selectively filled. This paper investigates the adsorption of limonene and α-pinene enantiomers on SU-MB. The framework demonstrated consistent enantioselectivity for both pairs of enantiomers, with a higher selectivity coefficient observed for α-pinenes than for limonenes. This difference arises from distinct trends in the isosteric heats of adsorption (Qst): for limonenes and (−)-α-pinene, Qst approaches the heat of liquefaction with increasing adsorption, whereas for (+)-α-pinene, Qst remains unchanged. These findings show that even a non-chiral crystal without chiral centers can exhibit enantioselectivity in adsorption processes, because of helical pores of one handedness.