Phosphine-Protected Atomically Precise Silver–Gold Alloy Nanoclusters and Their Luminescent Superstructures

Superstructures made by assemblies of metal nanoclusters (NCs) have gained interest due to their atomic precision and exciting photophysical properties. Although there are some reports of cluster-assembled materials of NCs protected with thiols, the preparation of stable thiol-free analogs is largely unexplored due to the poor stability of such structures. Herein, we report the synthesis of phosphine-protected alloy NCs of silver with varying gold doping and superstructures of such systems. We show that alloying of phosphine-protected silver clusters with gold results in comparatively more stable clusters than weakly ligated hydride- and phosphine-coprotected silver clusters. Two new Ag–Au alloy cluster series, [Ag11–xAux(DPPB)5Cl5O2]2+, where x = 1–10 (Ag11–xAux in short), and [Ag15–xAux(DPPP)6Cl5]2+, where x = 1–6 (Ag15–xAux in short), have been synthesized using two different phosphines, 1,4-bis(diphenylphosphino)butane (DPPB) and 1,3-bis(diphenylphosphino)propane (DPPP), respectively. These alloy clusters possess aggregation-induced emission (AIE) property, which was unexplored till now for phosphine-protected silver clusters. A visibly nonluminescent methanol solution of these clusters showed strong red luminescence in the presence of water due to the formation of cluster-assembled spherical hollow superstructures without any template. A solvophobic effect along with π···π and C–H···π interactions in the ligand shell make the alloy NCs assemble compactly within the hollow spheres. The assembly makes them highly emitting due to the restriction of intramolecular motion. The emissive states of the alloy clusters show a many-fold increase in lifetime in the presence of water. Femtosecond transient absorption studies revealed the lifetime of the excited-state charge carriers in their monomeric and aggregated states. Apart from enriching the limited family of phosphine-protected silver alloy NCs, this work also provides a new strategy to build a controlled assembly of NCs with tailored luminescence. These materials could be new phosphors for applications in composites, sensors, thin films, and photonic materials.