Electron transfer dynamics and excited state branching in a charge-transfer platinum(II) donor-bridge-acceptor assembly

A linear asymmetric Pt(II) trans-acetylide donor-bridge-acceptor triad designed for efficient charge separation, NAP=Pt(PBu3)(2)=Ph-CH2-PTZ (1), containing strong electron acceptor and donor groups, 4-ethynyl-N-octyl-1,8-naphthalimide (NAP) and phenothiazine (PTZ) respectively, has been synthesised and its photoinduced charge transfer processes characterised in detail. Excitation with 400 nm, similar to 50 fs laser pulse initially populates a charge transfer manifold stemming from electron transfer from the Pt-acetylide centre to the NAP acceptor and triggers a cascade of charge and energy transfer events. A combination of ultrafast time-resolved infrared (TRIR) and transient absorption (TA) spectroscopies, supported by UV-Vis/IR spectroelectrochemistry, emission spectroscopy and DFT calculations reveals a self-consistent photophysical picture of the excited state evolution from femto- to milliseconds. The characteristic features of the NAP-anion and PTZ-cation are clearly observed in both the TRIR and TA spectra, confirming the occurrence of electron transfer and allowing the rate constants of individual ET-steps to be obtained. Intriguingly, 1 has three separate ultrafast electron transfer pathways from a non-thermalised charge transfer manifold directly observed by TRIR on timescales ranging from 0.2 to 14 ps: charge recombination to form either the intraligand triplet (3)NAP with 57% yield, or the ground state, and forward electron transfer to form the full charge-separated state (CSS)-C-3 ((3)[PTZ(+)-NAP(-)]) with 10% yield as determined by target analysis. The (CSS)-C-3 decays by charge-recombination to the ground state with similar to 1 ns lifetime. The lowest excited state is (3)NAP, which possesses a long lifetime of 190 mu s and efficiently sensitises singlet oxygen. Overall, molecular donor-bridge-acceptor triad 1 demonstrates excited state branching over 3 different pathways, including formation of a long-distant (18 angstrom) full charge-separated excited state from a directly observed vibrationally hot precursor state.