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. 2025 Mar 24;16(18):7822-7828.
doi: 10.1039/d5sc00766f. eCollection 2025 May 7.

Light and protonation-controlled complex formation between sulfate ions and a stiff-stilbene based bis(cyclopeptide)

Stefan Mommer  1 , Benedict Wyrwol  2 , Jasper E Bos  1 , Stefan Kubik  2 , Sander J Wezenberg  1
Affiliations

Light and protonation-controlled complex formation between sulfate ions and a stiff-stilbene based bis(cyclopeptide)

Stefan Mommer et al. Chem Sci. .

Abstract

Anion-ligand coordination has been used to generate a number of supramolecular structures. Of particular interest is the transformation between different types of complexes using various stimuli. While there are multiple examples where this has been achieved with metal-ligand coordination complexes through incorporation of molecular photoswitches, the same has not yet been realized with anion-ligand coordination-driven assemblies. In this study, a sulfate-binding bis(cyclopeptide) with a photoswitchable stiff-stilbene linker is presented. Its (E)- and (Z)-isomers, and the different degrees of protonation of the anion (HSO4 - vs. SO4 2-), give rise to different assembly states. The accessible products have 1 : 1, 1 : 2 and 2 : 2 host-guest stoichiometries and can be interconverted by light irradiation and acid/base addition, resulting in a highly controllable responsive system that demonstrates the potential of sulfate coordination-driven supramolecular assembly.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Light- and protonation-controlled switching between stiff-stilbene-bridged bisCP in different isomeric and HSO4−/SO42− anion-complexed states.
Fig. 1
Fig. 1. (A) UV-vis spectral changes of (E)-bisCP in 0.5 vol% H2O/DMSO (10 μM) upon irradiation at 340 and 365 nm. (B) 1H NMR spectra of (E)-bisCP in 0.5 vol% H2O/DMSO-d6 (0.5 mM) (top), after irradiation at 340 nm (middle) and 365 nm (bottom).
Fig. 2
Fig. 2. 1H NMR spectra of (A) (E)-bisCP in 0.5 vol% H2O/DMSO-d6, (B) after the addition of 5 equiv. of TBA2SO4, (C) after the addition of acid (H2SO4) to exclusively form (E)-bisCP·(HSO4−)2, and (D) after the addition of base (DIPEA) to exclusively form [(E)-bisCP·SO42−]2.
Fig. 3
Fig. 3. Calculated structures of the 1 : 1 [(Z)-bisCP·SO42−] complex (A) and the 2 : 2 [(E)-bisCP]2·(SO42−)2 complex (B). All but the NH protons are omitted for reasons of clarity. The calculations were performed by using the MMFF force field followed by a DFT optimisation (B3LYP/6-31G*) of the obtained structures by using Spartan 24 (Wavefunction, Inc.).
Fig. 4
Fig. 4. 1H NMR spectral changes of (A) (E)-bisCP in 0.5 vol% H2O/DMSO-d6 (0.5 mM) in the presence of an excess of TBAHSO4 (2.5 mM) after irradiation with (B) 340 nm light and (C) consecutive irradiation with 365 nm light at 20 °C.
Fig. 5
Fig. 5. 1H NMR spectral changes of (A) (E)-bisCP in 0.5 vol% H2O/0.05 vol% DIPEA/DMSO-d6 (0.5 mM) in the presence of TBASO4 (2.5 mM) after irradiation with (B) 340 nm light and (C) consecutive irradiation with 365 nm light at 160 °C.
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