10.1021/jo301911w.s004 Ling Chen Ling Chen Heng-Yi Zhang Heng-Yi Zhang Yu Liu Yu Liu High Affinity Crown Ether Complexes in Water: Thermodynamic Analysis, Evidence of Crystallography and Binding of NAD<sup>+</sup> American Chemical Society 2012 monocationic pyridinium moiety NAD microcalorimetric titration crown ethers NMR experiments dinaphtho UV NADH equilibrium association constants tetrasulfonated High Affinity Crown Ether Complexes binding ability host molecule dicationic bipyridiniums 2012-11-02 00:00:00 Dataset https://acs.figshare.com/articles/dataset/High_Affinity_Crown_Ether_Complexes_in_Water_Thermodynamic_Analysis_Evidence_of_Crystallography_and_Binding_of_NAD_sup_sup_/2473135 Improving traditional crown ether to the water-soluble and high binding ability host molecule is critical to our efforts to model or mimic biological supramolecular systems. In this paper, we converted two traditional crown ethers, 1,5-dinaphtho-32-crown-8 and 1,5-dinaphtho-38-crown-10, into the water-soluble tetrasulfonated 1,5-dinaphtho-32-crown-8 and tetrasulfonated 1,5-dinaphtho-38-crown-10, evaluated their complexation with three dicationic bipyridiniums in aqueous solution by microcalorimetric titration, UV–vis, and NMR experiments, and then determined the crystal structures of three tetrasulfonatocrown ether-bipyridinium complexes. The equilibrium association constants of tetrasulfonated 1,5-dinaphtho-32-crown-8 with these bipyridiniums reach up to 10<sup>7</sup> M<sup>–1</sup>, while those of tetrasulfonated 1,5-dinaphtho-38-crown-10 are just in the range of 10<sup>5</sup> M<sup>–1</sup> order of magnitude. The thermodynamic data obtained show that the complexation of two tetrasulfonatocrown ethers with dicationic bipyridiniums is absolutely enthalpy-driven in water with an accompanying little entropic gain, and each monocationic pyridinium moiety in guest molecules can provide about −10 to −15 kJ·mol<sup>–1</sup> enthalpy contribution irrespective of the size of ether crowns. Moreover, we also investigated the recognition capability of the two water-soluble crown ethers with NAD<sup>+</sup> and NADH by microcalorimetric titration and NMR experiments, indicating that tetrasulfonated 1,5-dinaphtho-32-crown-8 shows exclusive selectivity to NAD<sup>+</sup>. The water-solubility and high affinity of this system as well as the flexible and non-preorganized characteristic of these crown ethers make it suitable to serve as a model for mimicking biological systems.