Scholarlink

<p>Chirality plays a central role in molecular recognition, and systems combining multiple, interdependent chiral elements can offer enhanced enantioselectivity. Here we show that covalent tethering of a dihydroxy-pillar[5]arene with <i>meso</i>-2,11-dibromododecanedioate yields diastereomeric <i>pseudo</i>[1]catenanes that combine three stereogenic features: two point chiral centers within the aliphatic linker, a helical chirality (<i>P</i>/<i>M</i>) induced by macrocycle closure, and a planar chirality of the pillararene ring. This system exhibits dynamic stereochemical behaviour involving <i>in</i>/<i>out</i> conformational equilibria, accompanied by inversion of the planar chirality. Using NMR spectroscopy, X-ray diffraction, DFT calculations and circular dichroism, we characterize the structures and dynamics of these macrobicyclic pillararenes, including guest-induced inclusion–exclusion processes. Hydrolysis affords a dicarboxyl-functionalized receptor capable of recognizing diamines via host-to-guest proton transfer, while enantiopure derivatives act as chiroptical sensors able to discriminate between L- and D-lysine esters. These results demonstrate how coupling multiple types of chirality can be exploited for responsive molecular recognition.</p><p></p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Enantioselective sensing driven by the interplay of point, helical and planar chirality in pillar[5]arene Pseudo[1]catenanes

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2025年12月14日

查看全文
  • Daniele Crisafulli,
  • Martina Mazzaferro,
  • Francesca Mancuso,
  • Roberto Cirilli,
  • Marco Pierini,
  • Roberto Zagami,
  • Luigi Monsù Scolaro,
  • Neal Hickey,
  • Silvano Geremia,
  • Anna Notti,
  • Melchiorre F. Parisi,
  • Ilenia Pisagatti,
  • Giuseppe Gattuso

摘要

Chirality plays a central role in molecular recognition, and systems combining multiple, interdependent chiral elements can offer enhanced enantioselectivity. Here we show that covalent tethering of a dihydroxy-pillar[5]arene with meso-2,11-dibromododecanedioate yields diastereomeric pseudo[1]catenanes that combine three stereogenic features: two point chiral centers within the aliphatic linker, a helical chirality (P/M) induced by macrocycle closure, and a planar chirality of the pillararene ring. This system exhibits dynamic stereochemical behaviour involving in/out conformational equilibria, accompanied by inversion of the planar chirality. Using NMR spectroscopy, X-ray diffraction, DFT calculations and circular dichroism, we characterize the structures and dynamics of these macrobicyclic pillararenes, including guest-induced inclusion–exclusion processes. Hydrolysis affords a dicarboxyl-functionalized receptor capable of recognizing diamines via host-to-guest proton transfer, while enantiopure derivatives act as chiroptical sensors able to discriminate between L- and D-lysine esters. These results demonstrate how coupling multiple types of chirality can be exploited for responsive molecular recognition.