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Updated: Sep 8, 2025

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Calix[n]azanediyldibenzoate: Intramolecular Hydrogen Bond-Assisted Synthesis, Acidichromism, and Oriented
Shuo Li1, Zhihao Lu1, Shuo Yan1
1School of Pharmaceutical and Chemical Engineering and Institute for Advanced Studies, Taizhou University, 1139 Shifu Road, Taizhou, Zhejiang 318000, China.
Abstract:
Here, intramolecular hydrogen bond (IMHBs)-induced rigidity is used for the first time to synthesize macrocyclic arenes. Calix[n]azanediyldibenzoates (C[n]A, where n = 3, 4, or 5) are synthesized through a one-step condensation reaction between dimethyl 2,2'-azanediyldibenzoate and paraformaldehyde. Compared to the monomer, the macrocycles exhibit a fast and significant acidochromic response due to the intramolecular charge transfer that is boosted by the synergistic effect of their adsorption and protonation. In particular, the specific 1,2-alternate conformer of C[4]A allows it to assemble into a one-dimensional channel in a portal to portal mode, which can be used for the oriented assembly of aromatic aldehydes. This study offers a new perspective for designing novel macrocyclic arenes and provides an important supramolecular example for stimulus-responsive materials and manipulating crystal orientation.
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