New Supramolecular Tecton: The Crucial Impact of the Polycation Charge and Geometry of H-Bonds on the Structure and Properties of Halometallates in the Solid State

Abstract

New tricationic organic supramolecular tecton has been designed and synthesized. Contrary to known mono- and dicationic species, this new molecule, being a “three-way connector”, allows assembling infinite supramolecular sheets and nets upon interaction with appropriate inorganic counterpart complex anions. In this work, triprotonated 6-amino-5,7-dimethyl-1,3-diazaadamantane, comprising two secondary and one primary nitrogen atoms, is utilized as a trication to form hybrid compounds with iodometallate anions by exercising five hydrogen bonds at the time. It is shown that the bulky cation works simultaneously as a spacer and a connector, such that the positions of inorganic [MI6]3− anions (M = Sb, Bi) in the crystal structures are defined by five hydrogen bonds and are well-separated from each other. The latter is considered as a prerequisite for the hybrid compounds to display optical properties originating from the undisturbed electronic structure of individual inorganic anions.