Self-Assembly of Atomically Precise Silver Nanoclusters in Crowded Colloids into Ultra-Long Ribbons with Tunable Supramolecular Chirality

Atomically precise metal nanoclusters (NCs) emerge as fascinating synthons in self-assembled materials. The self-assembly of metal NCs are highly sensitive to the environment because they have an inorganic-organic hybridized structure and a relatively complicated conformation. Here, it is shown that when confined in crowded colloids, a water-soluble Ag-9-cored nanocluster (Ag-9-NC) can self- assemble into ultra-long (up to millimeters) and photoluminescent ribbons with high flexibility. The ribbon contains rectangularly organized columns of Ag-9-NCs and can undergo secondary self-assembly to form bundled and branched structures. Formation of ribbons is observed in all the tested colloids, including lyotropic liquid crystals and disordered, three-dimensional network. The high viscosity/elasticity of the crowded colloids weakens gravity-induced sedimentation of the ribbons, leading to the formation of an interesting class of inorganic-organic composite materials where the hard Ag-containing skeleton strengthens the soft matter. The simultaneously occurring symmetry breaking during the self-assembly of Ag-9-NCs gives uncontrolled supramolecular chirality, which can be tuned through the majority rule and soldier-and-sergeant rule by the introduction of chiral seeds. The regulated chirality and the intrinsic photoluminescence of the Ag-9-NCs ribbons impart the composite material circularly polarized luminescence, opening the door for a variety of potential applications.