Self-Complementary Recognition of Supramolecular Urea - Aminotriazines in Solution and on Surfaces

The recognition of self-complementary quadruple urea–aminotriazine (UAT)-based hydrogen-bonded arrays was investigated in solution and at surfaces. For this purpose, an UAT-based donor–acceptor–donor–acceptor (DADA) array and complementary receptors were synthesized. Two-dimensional proton nuclear magnetic resonance (1H NMR) measurements in CDCl3 pointed at an intramolecular hydrogen-bond stabilization of the UAT, which promotes a planar molecular geometry and, thereby, results in a significant stabilization of the dimeric complex. The bond strength of the UAT dimers at surfaces was determined by atomic force microscopy-based single molecule force spectroscopy (AFM–SMFS) in hexadecane. The UAT receptor was immobilized on gold surfaces using an ultrathin layer of ethylene glycol terminated lipoic acid and isocyanate chemistry. The layers obtained and the reversible self-complementary recognition were thoroughly characterized with contact angle measurements, grazing angle Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and AFM. Loading rate-dependent SMFS measurements yielded a barrier width xβ and a bond lifetime at zero force toff(0) of 0.29 ± 0.02 nm and 100 ± 80 ms, respectively. The value of the corresponding off-rate constant koff suggests a substantially larger value of the dimerization constant compared to theoretical predictions, which is fully in line with the additional intramolecular hydrogen-bond stabilization detected in solution by 1H NMR spectroscopy.