Acenaphtho[1,2-d][1,2,3]triazole and Its Kuratowski Complex. A π-Extended Tecton for Supramolecular and Coordinative Self-assembly.

π-Extended acenaphtho[1,2- d ][1,2,3]triazoles, the unsubstituted Anta -H and its di- tert -butyl derivative Dibanta -H, as well as 5,6,7,8-tetrahydro-1 H -naphtho[2,3- d ][1,2,3]triazole Cybta -H were obtained in concise syntheses. In the solid state, Dibanta -H forms an unprecedented hydrogen-bonded cyclic tetrad, stabilized by dispersion interactions of the bulky t -Bu substituents, whereas a cyclic triad was in the crystal structure of Anta -H. These cyclic assemblies form infinite slipped stacks in the crystals. Evidence for analogous hydrogen-bonded self-assembly in solution was provided by low-temperature NMR spectroscopy and computational analyses. Kuratowski-type pentanuclear complexes [Zn 5 Cl 4 ( Dibanta ) 6 ] and [Zn 5 Cl 4 ( Cybta ) 6 ] were prepared from the respective triazoles. In the Dibanta complexes, the π-aromatic surfaces of the ligands extend from the edges of the tetrahedral Zn 5 core, yielding an enlarged structure with significant internal molecular free volume and red-shifted fluorescence.