10.1021/ja502295c.s001 Xuan-Feng Jiang Xuan-Feng Jiang Franky Ka-Wah Hau Franky Ka-Wah Hau Qing-Fu Sun Qing-Fu Sun Shu-Yan Yu Shu-Yan Yu Vivian Wing-Wah Yam Vivian Wing-Wah Yam From {Au<sup>I</sup>···Au<sup>I</sup>}‑Coupled Cages to the Cage-Built 2‑D {Au<sup>I</sup>···Au<sup>I</sup>} Arrays: Au<sup>I</sup>···Au<sup>I</sup> Bonding Interaction Driven Self-Assembly and Their Ag<sup>I</sup> Sensing and Photo-Switchable Behavior American Chemical Society 2014 Electronic absorption aurophilic interactions supramolecular assemblies cage emission studies 8L array AuI TDCC AgI cation 2014-08-06 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/From_Au_sup_I_sup_Au_sup_I_sup_Coupled_Cages_to_the_Cage_Built_2_D_Au_sup_I_sup_Au_sup_I_sup_Arrays_Au_sup_I_sup_Au_sup_I_sup_Bonding_Interaction_Driven_Self_Assembly_and_Their_Ag_sup_I_sup_Sensing_and_Photo_Switchable_Behavior/2560306 Metal–metal bonding interactions have been used to generate a number of unique supramolecular assemblies with fascinating functions. We presented here a new class of gold­(I)-containing metallosupramolecular cages and cage-built two-dimensional (2-D) arrays of {Au<sub>8</sub>L<sub>2</sub>}<sub><i>n</i></sub> (<i>n</i> = 1 or ∞, L = tetrakis-dithiocarbamato-calix[4]­arene, TDCC), <b>1</b>–<b>3</b>, which are constructed from the self-assembly of deep-cavitand calix[4]­arene-based supramolecular cages consisting of octanuclear Au­(I) motifs. Synchrotron radiation X-ray diffraction structural analyses of <b>1</b>–<b>3</b> revealed their quadruple-stranded helicate dimeric cage structure and the presence of 2-D arrays of cages linked together by inter- and intramolecular Au<sup>I</sup>···Au<sup>I</sup> interactions. Electronic absorption and emission studies of complexes <b>1</b>–<b>3</b> indicated the occurrence of a programmable self-assembly process in a concentration-dependent stepwise manner with the links built via aurophilic interactions. These novel gold­(I) supramolecular cages exhibited green phosphorescence and have been shown to serve as highly selective proof-of-concept luminescent sensors toward Ag<sup>I</sup> cation among various competitive transition-metal ions.