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.