Hierarchical Self-Assembly of Cyclic Dye Arrays into Two-Dimensional Honeycomb Nanonetworks

A study was conducted to demonstrate hierarchical self-assembly of cyclic dye arrays into two-dimensional (2D) honeycomb nanonetworks. The cyclic array was prepared on a semipreparative scale, using stoichiometric amounts of perylene tetracarboxylic bisimide (PBI) ligand and zinc(II) triflate in 90% yield, after formation of metallocycle was confirmed by H NMR titration and DOSY investigations. Significant structural characterization of the macrocycle was also achieved by matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS), providing expected mass peak of of trimer metallocycle and additional peaks of multicharged fragments. It was observed that the metallocycle array was soluble in dimethylformamide (DMF) and chloroform/acetonitrile mixture, while the solutions remain clear for a long time without forming any precipitation.