A DNA strand can
encapsulate a silver molecule to create a nanoscale,
aqueous stable chromophore. A protected cluster that strongly fluoresces
can also be weakly photolabile, and we describe the laser-driven photochemistry
of the green fluorophore C
4
AC
4
TC
3
GT
4
/Ag
10
6+
. The embedded cluster
is selectively photoexcited at 490 nm and then bleached, and we describe
how the efficiency, products, and route of this photochemical reaction
are controlled by the DNA cage. With irradiation at 496.5 nm, the
cluster absorption progressively drops to give a photodestruction
quantum yield of 1.5 (±0.2) × 10
–4
, ∼10
3
× less efficient than fluorescence. A new λ
abs
= 335 nm chromophore develops because the precursor with
4 Ag
0
is converted into a group of clusters with 2 Ag
0
– Ag
6
4+
, Ag
7
5+
, Ag
8
6+
, and Ag
9
7+
. The 4–7 Ag
+
in this series are chemically distinct
from the 2 Ag
0
because they are selectively etched by iodide.
This halide precipitates silver to favor only the smallest Ag
6
4+
cluster, but the larger clusters re-develop
when the precipitated Ag
+
ions are replenished. DNA-bound
Ag
10
6+
decomposes because it is electronically
excited and then reacts with oxygen. This two-step process may be
state-specific because O
2
quenches the red luminescence
from Ag
10
6+
. However, the rate constant of 2.3
(±0.2) × 10
6
M
–1
s
–1
is relatively small, which suggests that the surrounding DNA matrix
hinders O
2
diffusion. On the basis of analogous photoproducts
with methylene blue, we propose that a reactive oxygen species is
produced and then oxidizes Ag
10
6+
to leave behind
a loose Ag
+
-DNA skeleton. These findings underscore the
ability of DNA scaffolds to not only tune the spectra but also guide
the reactions of their molecular silver adducts.