Stimuli-Responsive and Structure-Adaptive Three-Dimensional Gold(I) Cluster Cages Constructed via "De-aurophilic" Interaction Strategy.

Self-assembly of three-dimensional (3D) metallosupramolecular cages has drawn increasing attention for their potential to interconvert between different architectures due to the dynamic and reversible features of the coordination bond. These supramolecular transformations can provide unique approaches for the construction of stimuli-responsive supramolecular model systems to mimic biological transformation processes. While gold(I) clusters have attracted much interest due to their propensity to exhibit aurophilic interactions, the construction of 3D gold(I) cluster cages has remained a challenging and daunting task. Here, we proposed a "de-aurophilic" interaction strategy, which involves the prevention of aurophilic interaction formation between the basic [(μ3-S)Au3]+ units, to construct 3D gold(I) cluster cages. Through the judicious design of diphosphine ligands, an unprecedented class of gold(I) cluster cages with adaptive structures has been constructed. These gold(I) cluster cages are found to show intriguing stimuli-responsive structure transformation and interconversion. This work not only provides a strategy for the design and construction of novel 3D supramolecular cages based on cluster nodes but also offers a paradigm to study the stimuli-responsive structural interconversion between the unique structures of these gold(I) cluster cages.