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

Abstract 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.