Chloride Ligands on DNA-Stabilized Silver Nanoclusters

[Image: see text] 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)[Ag(16)Cl(2)](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 (35)Cl-nuclear magnetic resonance spectrum of (DNA)(2)[Ag(16)Cl(2)](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)[Ag(16)Cl(2)](8+). Using the unusual stability of (DNA)(2)[Ag(16)Cl(2)](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.