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Pseudo-nanophase separation, enabled by noncovalently grafted sidechains, offers a promising approach for constructing high-performance membranes, featuring rapid ion transport, robust chemical stability, and simplified manufacturing. However, striking a balance between ionic conductivity and mechanical/chemical stability proves challenging since excessive hydrophilic grafting leads to overswelling and compromised integrity of the membranes, rendering them unsuitable for demanding applications like vanadium redox flow batteries (VRFBs). In this study, we describe a new approach for achieving high-performance VRFB membranes via employing polymer as supramolecular sidechains, rather than small molecules. This strategy achieves remarkable pseudo-nanophase separation while minimizing the utilization of functional (hydrophilic) sites. As a result, the resulting membranes exhibit exceptional robustness and proton conductivity, with an extraordinarily low area resistance of merely 0.11 Ω cm2, thus circumventing the prevailing trade-off between ionic conductivity and mechanical/chemical stability. Ultimately, VRFBs integrated with these membranes achieve energy efficiencies up to 80 % even at high current densities of 240 mA cm−2, accompanied by a remarkably low capacity decay rate of 0.064 % per cycle during long-cycle tests. This work not only achieves ultra-high conductivity with minimal functional groups, but also advances pseudo-nanophase separation strategies and provides valuable insights into optimized utilization of limited functional groups in membrane design. [Display omitted] • Polymers are proposed as supramolecular sidechains. • Underlying interaction mechanism is elucidated by experimental and simulation study. • A minimal number of hydrophilic sites enable noteworthy pseudo-nanophase separation. • Prevailing conductivity-mechanical/chemical stability trade-off is circumvented. • A VRFB with high efficiencies and slow capacity decay of 0.064 %/cycle is attained. [ABSTRACT FROM AUTHOR]

Crystalline supramolecular architectures mediated by cations, anions, ion pairs or neutral guest species are well established. However, the robust crystallization of a well-designed receptor mediated by labile anionic solvate clusters remains unexplored. Herein, we describe the synthesis and crystalline behaviors of a trimacrocyclic hexasubstituted benzene 2 in the presence of guanidium halide salts and chloroform. Halide hexasolvate clusters, viz. [Cl(CHCl 3 ) 6 ] - , [Br(CHCl 3 ) 6 ] - , and [I(CHCl 3 ) 6 ] - , were found to be critical to the crystallization process, as suggested by the single-crystal structures, X-ray powder diffraction (XRPD), thermogravimetric analysis (TGA), scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS), and NMR spectroscopy. This study demonstrates the hitherto unexpected role that labile ionic solvate clusters can play in stabilizing supramolecular architectures., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)