Synthesis of a New Copper-Azobenzene Dicarboxylate Framework in the Form of Hierarchical Bulk Solids and Thin Films without and with Patterning

Reaction of copper(II) acetate with azobenzene-4,4′-dicarboxylic acid results in the formation of a metal–organic framework with the unexpected stoichiometry of Cu(II):ligand of 2:1. The bulk synthesis results in microspheres assembled from either nanobricks or nanoflakes, depending on the ratio of the reactants in solution. While the former behaves like a bulk solid with clear reflections in the X-ray and electron diffraction experiments, the latter obviously is dominated by surface effects, with a significant fraction of slightly expanded elemental cells and a significantly increased outer surface area. The material could also be deposited on a variety of surfaces using a stepwise layer-b…