Rational design of an acceptor-chromophore-relay-catalyst tetrad assembly for water oxidation.

We report the step-by-step synthesis of a precious metal-free acceptor-chromophore-relay-catalyst tetrad assembly that exhibits a turnover frequency (TOF) of 7.5 × 10 s under neutral conditions. Transient absorption spectroscopic studies indicate that upon fullerenol incorporation into the investigated complexes, charge separation efficiency increases considerably.

Long-Lived Charge-Transfer State in Spiro Compact Electron Donor-Acceptor Dyads Based on Pyromellitimide-Derived Rhodamine: Charge Transfer Dynamics and Electron Spin Polarization.

We observed a long-lived charge transfer (CT) state in a novel orthogonal compact electron donor-acceptor dyads, with closed form of rhodamine (Rho) as electron donor and pyromellitimide (PI),or thionated PI, as electron acceptor. The two parts in the dyads are connected via a spiro quaternary carbon atom, thus the torsion between the donor and acceptor is completely inhibited, which is beneficial to reduce the reorganization energy and to exploit the Marcus inverted region effect to prolong the CT state lifetime. Femtosecond transient absorption spectra show that the charge separation is rather fast, while nanosecond transient absorption spectra confirmed the formation of long-lived CT state (2.