Self-assembly of a functional cryptand core（1） having six dithiocarbamate groups and \{（dppm）Au2Cl\}2 in methanol followed by the addition of excess NH4PF6 affords a novel metallodendritic supramolecule（2）. This dendritic supramolecule was characterized by NMR, MS, XPS, IR, UV-Vis, luminescence spectra and elemental analyses. The results show the concentration-dependent absorption and luminescent properties in acetonitrile solution for the title compound, which may be closely related to the intramolecular and intermolecular aggregation of digold（Ⅰ） branches through Au（Ⅰ）…Au（Ⅰ） interactions.
