Numerous studies
have explored the kinetics of light-induced
charge
separation and thermal charge recombination in donor–acceptor
compounds, but quantum efficiencies have rarely been investigated.
Here, we report on two essentially isomeric molecular triads, both
comprising a π-extended tetrathiafulvalene (ExTTF) donor, a
ruthenium(II)-based photosensitizer, and a naphthalene diimide (NDI)
acceptor. The key difference between the two triads is how the NDI
acceptor is connected. Linkage at the NDI core provides stronger electronic
coupling to the other molecular components than connection via the
nitrogen atoms of NDI. This change in molecular connectivity is expected
to accelerate both energy-storing charge separation and energy-wasting
charge recombination processes, but it is not a priori clear how this
will affect the triad’s ability to store photochemical energy;
any gain resulting from faster charge separation could potentially
be (over)compensated by losses through accelerated charge recombination.
The new key insight emerging from our study is that the quantum yield
for the formation of a long-lived charge-separated state increases
by a factor of 5 when going from nitrogen- to core-connected NDI,
providing the important proof of concept that better molecular connectivity
indeed enables more efficient photochemical energy storage. The physical
origin of this behavior seems to root in different orbital connectivity
pathways for charge separation and charge recombination, as well as
in differences in the relevant orbital interactions depending on NDI
connection. Our work provides guidelines for how to discriminate between
energy-storing and energy-wasting electron transfer reactions in order
to improve the quantum yields for photochemical energy storage and
solar energy conversion.