DNA serves as a versatile template for few-atom silver clusters and their organized self-assembly. These clusters possess unique structural and photophysical properties that are programmed into the DNA template sequence, resulting in a rich palette of fluorophores which hold promise as chemical and biomolecular sensors, biolabels, and nanophotonic elements. Here, we review recent advances in the fundamental understanding of DNA-templated silver clusters (Ag _N -DNAs), including the role played by the silver-mediated DNA complexes which are synthetic precursors to Ag _N -DNAs, structure-property relations of Ag _N -DNAs, and the excited state dynamics leading to fluorescence in these clusters. We also summarize the current understanding of how DNA sequence selects the properties of Ag _N -DNAs and how sequence can be harnessed for informed design and for ordered multi-cluster assembly. To catalyze future research, we end with a discussion of several opportunities and challenges, both fundamental and applied, for the Ag _N -DNA research community. A comprehensive fundamental understanding of this class of metal cluster fluorophores can provide the basis for rational design and for advancement of their applications in fluorescence-based sensing, biosciences, nanophotonics, and catalysis.

DNA oligomers are known to serve as stabilizing ligands for silver nanoclusters (Ag_N-DNAs) with rod-like nanocluster geometries and nanosecond-lived fluorescence. Here, we report two Ag_N-DNAs that possess distinctly different structural properties and are the first to exhibit only microsecond-lived luminescence. These emitters are characterized by significant broadband downconversion from the ultraviolet/visible to the near-infrared region. Circular dichroism spectroscopy shows that the structures of these two Ag_N-DNAs differ significantly from previously reported Ag_N-DNAs. We find that these nanoclusters contain eight valence electrons, making them the first reported DNA-stabilized luminescent quasi-spherical superatoms. This work demonstrates the important role that nanocluster composition and geometry play in dictating luminescence properties of Ag_N-DNAs and significantly expands the space of structure-property relations that can be achieved for Ag_N-DNAs.

DNA-stabilized silver nanoclusters (Ag_N-DNAs) are known to have one or two DNA oligomer ligands per nanocluster. Here, we present the first evidence that Ag_N-DNA species can possess additional chloride ligands that lead to increased stability in biologically relevant concentrations of chloride. Mass spectrometry of five chromatographically isolated near-infrared (NIR)-emissive Ag_N-DNA species with previously reported X-ray crystal structures determines their molecular formulas to be (DNA)₂[Ag₁₆Cl₂]⁸⁺. Chloride ligands can be exchanged for bromides, which red-shift the optical spectra of these emitters. Density functional theory (DFT) calculations of the 6-electron nanocluster show that the two newly identified chloride ligands were previously assigned as low-occupancy silvers by X-ray crystallography. DFT also confirms the stability of chloride in the crystallographic structure, yields qualitative agreement between computed and measured UV-vis absorption spectra, and provides interpretation of the ³⁵Cl-nuclear magnetic resonance spectrum of (DNA)₂[Ag₁₆Cl₂]⁸⁺. A reanalysis of the X-ray crystal structure confirms that the two previously assigned low-occupancy silvers are, in fact, chlorides, yielding (DNA)₂[Ag₁₆Cl₂]⁸⁺. Using the unusual stability of (DNA)₂[Ag₁₆Cl₂]⁸⁺ in biologically relevant saline solutions as a possible indicator of other chloride-containing Ag_N-DNAs, we identified an additional Ag_N-DNA with a chloride ligand by high-throughput screening. Inclusion of chlorides on Ag_N-DNAs presents a promising new route to expand the diversity of Ag_N-DNA structure-property relationships and to imbue these emitters with favorable stability for biophotonics applications.