Nonradiative\nDeactivation of the Fluorescent Ag<sub>16</sub>-DNA and Ag<sub>10</sub>-DNA Emitters: The Role of Water

The luminescent quantum yield of silver-cluster emitters\nstabilized\nby short oligonucleotides (Ag<sub>N</sub>-DNA) may be efficiently\ntuned by replacing nucleobases in their stabilization DNA matrices\nwith analogues. In the present study, we proposed a valuable and straightforward\ntheoretical methodology for assessing the photophysical behaviors\nemerging in Ag<sub>N</sub>-DNA emitters after excitation. Using green\nAg<sub>10</sub>-DNA and near-IR Ag<sub>16</sub>-DNA emitters we demonstrate\nhow point guanine/inosine replacement could affect the photophysical\nrate constants of radiative/nonradiative processes. The main deactivation\nchannel of the fluorescence of Ag<sub>16</sub>-DNA is intersystem\ncrossing, which is in line with experimental data, whereas for Ag<sub>10</sub>-DNA the calculations overestimate the intersystem crossing\nrate possibly due to pure solvent contributions.