Dicarboxylate recognition based on ultracycle hosts through cooperative hydrogen bonding and anion-π interactions

Wen-Hui Mi; Teng-Yu Huang; Xu-Dong Wang; Yu-Fei Ao; Qi-Qiang Wang; De-Xian Wang

doi:10.3762/bjoc.21.72

Dicarboxylate recognition based on ultracycle hosts through cooperative hydrogen bonding and anion-π interactions

Beilstein J Org Chem. 2025 May 6:21:884-889. doi: 10.3762/bjoc.21.72. eCollection 2025.

Authors

Wen-Hui Mi^#^{1

2}, Teng-Yu Huang^#¹, Xu-Dong Wang¹, Yu-Fei Ao^{1

2}, Qi-Qiang Wang^{1

2}, De-Xian Wang^{1

2}

Affiliations

¹ Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
² University of Chinese Academy of Sciences, Beijing 100049, China.

^# Contributed equally.

Abstract

The efficient binding of dicarboxylates represents an important yet challenging issue in supramolecular chemistry. In this study, we designed functional ultracycles as hosts to accommodate large organic dicarboxylate anions. These ultracycles were synthesized via a one-pot strategy starting from macrocyclic precursors. Host-dicarboxylate binding was investigated using ¹H NMR titrations, revealing that B4aH exhibits strong binding affinities toward a series of dicarboxylates, with association constants reaching up to 6896 M^-1. The selectivity for heptanedioate (C7 ^2- ) was attributed to cooperative hydrogen bonding, anion-π interactions, and a size-matching effect, as supported by DFT optimizations.

Keywords: anion recognition; anion–π interactions; dicarboxylates; hydrogen bonding; ultracycles.

Publication types

Letter