The complex stability constants (K(S)) and thermodynamic parameters (DeltaH degrees and TDeltaS degrees) for 1:1 intermolecular complexation of three water-soluble calixarenes, that is, p-sulfonato calix[4]arene (C4AS), p-sulfonato thiacalix[4]arene (TCAS), and p-sulfonato calix[5]arene (C5AS), with dipyridines (4-DPD and 2-DPD) and 1,10-phenanthroline (Phen) have been determined by means of titration microcalorimetry in an acidic buffer solution (pH = 2.0) at 298.15 K, and their binding modes have been investigated by (1)H NMR and 2D ROESY NMR spectroscopy. The results obtained indicate that 4-DPD, 2-DPD, and Phen are included in the cavity of C5AS with the different patterns, this is, accumbent for 4-DPD, acclivitous for 2-DPD and Phen, while Phen is included upright in the cavity of C4AS. The K(S) values decrease with increasing cavity size of host molecules but enhance with extending conjugation degree of guest molecules, and thus C4AS exhibits an exceptionally high Phen/4-DPD selectivity of 22.5. Thermodynamically, the complexation of DPDs/Phen with the water-soluble calixarenes is obviously enthalpy-driven, but the molecular selectivity is mainly governed by the entropy term.

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The complex stability constants (Ka) and thermodynamic parameters (DeltaG degrees, DeltaH degrees, and TDeltaS degrees) for 1:1 complexation of water-soluble calix[4]arene, thiacalix[4]arene, and calix[5]arene sulfonates with pyridine and their methylated derivatives have been determined by means of isothermal titration calorimetry at pH 2.0 and 7.2 at 298.15 K, and their binding modes have been investigated by NMR spectroscopy. The results obtained show that sulfonatocalixarenes afford stronger binding ability toward pyridine guests at pH 2.0, attributable to the positive electrostatic interactions and the more extensive desolvation effects, but present higher molecular selectivity at pH 7.2 owing to the strengthened C-H...pi interactions. The pH-responsible binding ability and molecular selectivity are discussed from the viewpoint of electrostatic, pi-stacking, van der Waals interactions and size-fit relationship between host and guest. A close comparison further demonstrates that the C-H...pi interactions and van der Waals interactions play a more important role than pi...pi interactions in the present inclusion complexation.

Supramolecular plastics (SMPs) can be made mechanically robust, repairable, and recyclable, rendering themselves promising alternatives to their conventional predecessors to address environmental concerns. However, dense accumulations of noncovalent bonds generally lead to mechanical brittleness as well as intolerance toward heat and moisture. To resolve this issue, a simple strategy of preparing high-performance SMP by constructing highly dense, but irregular hydrogen-bond networks with hierarchical structures is proposed. The resultant SMP exhibits an outstanding combination of good comprehensive mechanical properties (high stiffness, strength, and toughness with ductile failure when fracturing), excellent dynamic behaviors (repairability and recyclability), and high tolerances toward moisture and high temperatures (as high as 90 °C). Additionally, the SMP also shows a high dielectric constant, exhibiting great potential for applications such as healable flexible touch screens and energy storage. Last, through structure characterizations and molecular dynamic simulation, this study provides a fundamental insight into the mechanism behind such high-performances from nano-to micro-scales, which is expected to inspire the design of a wide range of other SMPs that use different chemistries.

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