Chemical Physics Letters, Vol.691, 163-168, 2018
Direction-dependent secondary bonds and their stepwise melting in a uracil-based molecular crystal studied by infrared spectroscopy and theoretical modeling
Three types of supramolecular interactions are identified in the three crystallographic directions in crystals of 1,4-bis[(1-hexylurac-6-yl) ethynyl] benzene, a uracil-based molecule with a linear backbone. These three interactions, characterized by their strongest component, are: intermolecular double H-bonds along the molecular axis, London dispersion interaction of hexyl chains connecting these linear assemblies, and p-p stacking of the aromatic rings perpendicular to the molecular planes. On heating, two transitions happen, disordering of hexyl chains at 473 K, followed by H-bond melting at 534 K. The nature of the bonds and transitions was established by matrix-isolation and temperature-dependent infrared spectroscopy and supported by theoretical computations. (C) 2017 Elsevier B.V. All rights reserved.