The conversion of solar energy into
chemical fuel represents
a
capstone goal of the 21st century and has the potential to supply
terawatts of power in a globally distributed manner. However, the
disparate time scales of photodriven charge separation (∼fs)
and steps in chemical reactions (∼μs) represent an inherent
bottleneck in solar-to-fuels technology. To address this discrepancy,
we are developing earth-abundant coordination complexes that undergo
light-induced conformational rearrangements such that charge separation
(CS) is hastened, while charge recombination (CR) is slowed. To these
ends, we report the preparation and characterization of a new series
of conformationally fluxional copper coordination complexes that contain
a twisted intramolecular charge transfer (TICT) fluorophore as part
of their ligand scaffold. Structural and spectroscopic characterization
of the Cu(I) and Cu(II) complexes formed with these ligands in their
ground states establish oxidation state-dependent conformational dynamicity,
while time-resolved emission and transient absorption spectroscopies
define the photophysical parameters of photo-induced excited states.
Building on initial reports with a related set of molecules, the improved
ligand design presented here greatly simplifies the observed photophysics,
effectively shutting down unwanted ligand-centered excited states
previously observed. Time-dependent density functional theory (TDDFT)
analyses reveal an unusual metal-to-TICT electronic transition only
reported once before, and though the formation of a CS state is not
observed directly through experiments, TDDFT geometry optimizations
in the excited states support the formation of transient Cu(II) CS
species, lending credence to the potential success of our approach.
These studies establish a clear model for the excited state dynamics
at play in proof-of-concept systems and clarify key design parameters
for future optimizations toward achieving long-lived CS via photoinduced
conformational gating.