Electronic Supporting Data: Aromatic Wall Extension of Glycoluril-Derived Molecular Clips Enhances Binding of Planar Aromatic Dyes

Abstract

We report the synthesis and characterization of a new methylene bridged glycoluril dimer featuring anthracene walls (H2). H2 displays good solubility in water (≥7 mM) but undergoes self-association at concentrations above 2 mM. 1H NMR experiments establish that H2 binds cationic dyes inside its cavity with a -stacked geometry that places the cationic residues at the ureidyl carbonyl portals of H2. The binding constants of both naphthalene-walled clip H1 and anthracene-walled clip H2 toward a panel of dyes were measured by direct or competitive UV/Vis or fluorescence titrations in phosphate buffered saline (PBS). Binding constants cover the range from 103 – 108 M-1. Dyes that feature cationic NMe2 groups bind more strongly than analogous dyes with cationic NH2 groups. We find that pi-extension of the aromatic walls from H1 to H2 generally results in an ≈ 10-fold increase in binding affinity. Host•guest complexes of H1 and H2 with planar cationic dyes benefit from substantial cation-pi interactions.