Long-lived Ag₁₀ ⁶⁺ luminescence and a split DNA scaffold

Molecular silver clusters emit across the visible to near-infrared, and specific chromophores can be formed using DNA strands. We study C₄AC₄TC₃G that selectively coordinates and encapsulates Ag₁₀ ⁶⁺, and this chromophore has two distinct electronic transitions. The green emission is strong and prompt with ϕ = 18% and τ = 1.25 ns, and the near-infrared luminescence is weaker, slower with τ = 50 µs, and is partly quenched by oxygen, suggesting phosphorescence. This lifetime can be modulated by the DNA host, and we consider two derivatives of C₄AC₄TC₃G with similar sequences but distinct structures. In one variant, thymine was excised to create an abasic gap in an otherwise intact strand. In the other, the covalent phosphate linkage was removed to split the DNA scaffold into two fragments. In relation to the contiguous strands, the broken template speeds the luminescence decay by twofold, and this difference may be due to greater DNA flexibility. These modifications suggest that a DNA can be structurally tuned to modulate metastable electronic states in its silver cluster adducts.