Pyridinebisthiazolamine-Strapped Calix[4]pyrrole: An Anion Receptor Selectively Binding Dihydrogenphosphate via Simultaneous Proton Transfer Events

doi:10.6023/cjoc202510016

Abstract

The binding interactions between various test anions and the pyridinebisthiazolamine-strapped calix[4]pyrrole (2) were investigated in CH₃CN solution via ¹H NMR and UV-vis spectroscopic analyses. The results demonstrated that receptor 2 exhibits high affinity and selectivity toward dihydrogenphosphate (${{\text{H}}_{2}}\text{PO}_{4}^{}$). On the basis of ¹H NMR spectroscopic analyses and density functional theory (DFT) calculations, it was concluded that simultaneous proton transfer events occur between receptor 2 and ${{\text{H}}_{2}}\text{PO}_{4}^{}$ during the recognition process, where one thiazole nitrogen is protonated to form a hydrogen bond donor and the thiazole-linked NH is deprotonated to generate a hydrogen bond acceptor. Furthermore, receptor 2 acts as a pH-controlled molecular switch for anion recognition: it binds ${{\text{H}}_{2}}\text{PO}_{4}^{}$ preferentially under neutral conditions and switches to $\text{HSO}_{4}^{}$ binding under acidic conditions, which is enabled by the pH-responsive protonation/deprotonation of the thiazole moieties in the strap.

Key words: calix[4]pyrrole, anion recognition, dihydrogenphosphate, proton transfer

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Yanmei Yan, Ruiping Huo, Yingchun He. Pyridinebisthiazolamine-Strapped Calix[4]pyrrole: An Anion Receptor Selectively Binding Dihydrogenphosphate via Simultaneous Proton Transfer Events[J]. Chinese Journal of Organic Chemistry, 2026, 46(6): 2442-2449.

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Fig. & Tab. 6

Figure 1. (a) Chemical structures of receptors 1 and 2; (b) Hydrogen phosphate binding mode in the pyridinebisthiazolamine- strapped calix[4]pyrrole 2 in its protonated form discovered previously by our group[16]; (c) Dihydrogenphosphate binding mode in the pyridinebisthiazolamine-strapped calix[4]pyrrole 2

Scheme 1. Preparation of pyridinebisthiazolamine-strapped calix[4]pyrrole 2

Figure 2. 1H NMR (600 MHz) spectra of 2 (2.0 mmol/L) upon the addition of TBAH2PO4 in CD3CN (receptor: a~f, ${{\text{H}}_{2}}\text{PO}_{4}^{}$ complex: a'~f') 1H NMR δ

Figure 3. (Left) Computed simultaneous proton transfer transition states TS1 with M062X density functional (def2tzvp level) (The relative electronic energy barriers (ΔE) in acetonitrile solvent are given in kJ/mol); (Right) The optimized molecular structure of receptor 2 with dihydrogenphosphate as calculated in CH3CN

Figure 4. 1H NMR (CD3CN, 600 MHz) spectra of 2 in the presence of 1 equiv. of various anions 1H NMR δ

Figure 5. Partial 1H NMR spectra of receptor 2 (2.0 mmol/L in CD3CN) ¹H NMR δ (a) Free receptor; (b) in the presence of 1.0 equiv. TBAH2PO4; (c) after adding 1.0 equiv. TBAHSO4 to (b); (d) after adding 1.5 equiv. HNO3 to (c); (e) after further adding 1.5 equiv. TBAOH to (d); (f) after further adding 1.5 equiv. HNO3 to (e); (g) in the presence of 1.0 equiv. TBAHSO4 and 1.5 equiv. HNO3; (h) in the presence of 1.0 equiv. TBAHSO4.

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