DNA-stabilized silver
nanoclusters (AgN-DNAs)
are known
to have one or two DNA oligomer ligands per nanocluster. Here, we
present the first evidence that AgN-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 AgN-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 AgN-DNAs, we identified an additional AgN-DNA with
a chloride ligand by high-throughput screening. Inclusion of chlorides
on AgN-DNAs presents a promising new route to expand the
diversity of AgN-DNA structure–property relationships
and to imbue these emitters with favorable stability for biophotonics
applications.