(Keynote) Radical Ion Excited States As Super-Redox Agents for Artificial Photosynthesis
Authors: Wasielewski Michael R 
Published: December 2020

We will discuss several examples in which photoexcitation of a stable radical anion or cation with visible or NIR light results in production of a high-potential radical ion excited state that can carry out difficult redox reactions relevant to artificial photosynthesis.
First, we will show that selective excitation of a naphthalenediimide radical anion (NDI•−) covalently linked to the 4-, 5, or 6-positions of the bipyridine (bpy) in the Re(bpy)(CO)3X (X = Cl or pyridine) carbon dioxide reduction catalyst results in electron transfer from 2*NDI•− to Re(bpy)(CO)3X to form Re(bpy•−)(CO)3X, the first intermediate in the photocatalytic reduction of CO2. Femtosecond UV/Vis, near-IR and mid-IR spectroscopy on these constitutional isomers show that systematically varying the electronic coupling as well as the reaction free energy increases the lifetime of Re(bpy•−)(CO)3X by an order of magnitude when the NDI chromophore is attached to the 6-position of bpy.
Electrochemical reduction of the corresponding Mn(bpy)(CO)3X CO2 reduction catalyst is thought to proceed by the initial reduction of MnI to Mn0. We have covalently attached a naphthalenediimide radical anion (NDI•-) chromophore to the 4-, 5-, or 6-positions of the bpy via a phenyl bridge to produce Mn(NDI•--bpy)(CO)3X, where X = Br, CH3CN, or DMF, and have used femtosecond and nanosecond transient IR spectroscopy to directly observe the intermediates produced by two electron transfer reactions following selective photo-excitation of NDI•−. In complexes where NDI•− is attached at the 4- or 5-positions of bipyridine, only the reaction Mn(2*NDI•−-bpy)(CO)3X → Mn(NDI-bpy•−)(CO)3X is observed, while in the complex where NDI•− is attached to the 6-position of bipyridine, the reaction sequence: Mn(2*NDI•−-bpy)(CO)3X → Mn(NDI-bpy•−)(CO)3X → Mn0(NDI-bpy)(CO)3 is observed. Moreover, in the complexes with an NDI•- bound to the 6-position of bipyridine, Mn0(NDI-bpy)(CO)3 exhibits a lifetime that is ~105 times longer than those in complexes with an NDI•- bound at the 4- or 5- positions of the bipyridine.
On the oxidative side, we will discuss the 10-phenyl-10H-phenothiazine radical cation (PTZ+•), which has a manifold of excited doublet states accessible using visible and NIR light that can serve as super-photo-oxidants with excited state potentials is excess of +2.1 V vs SCE to power energy demanding oxidation reactions. Photo-excitation of PTZ+• in CH3CN with a 517 nm laser pulse populates a Dn electronically excited doublet state that decays first to the unrelaxed lowest electronic excited state, D1' (τ < 0.3 ps), followed by relaxation to D1 (τ = 10.9 ± 0.4 ps), which finally decays to D0 (τ = 32.3 ± 0.8 ps). D1' can also be populated directly using a lower energy 900 nm laser pulse, which results in a longer D1' → D1 relaxation time (τ = 19 ± 2 ps). To probe the oxidative power of PTZ+• photoexcited doublet states, PTZ+• was covalently linked to each of three hole acceptors, perylene (Per), 9,10-diphenyl-anthracene (DPA), and 10-phenyl-9-anthracene-carbonitrile (ACN), which have oxidation potentials of 1.04, 1.27, and 1.6 V vs. SCE, respectively. In all cases, photoexcitation of PTZ+• result in ultrafast oxidation of Per, DPA, and ACN.
The photoexcited peri-xanthenoxanthene radical cation (PXX+•) is another super-oxidant that has a 124 ps electronic excited state (D1) lifetime and can deliver +2.1 V vs. SCE of oxidizing potential. Photoexcitation of PXX+• covalently attached to electron deficient 9,10-bis(trifluoromethyl)anthracene (TMFA) using an 885 nm laser pulse drives oxidation of TFMA with unity quantum yield. Extending the PXX+•-TFMA dyad to a molecular triad having a 9,10-diphenylanthracene terminal hole acceptor, PXX+•-TFMA-DPA, and selectively exciting PXX+• results in formation of PXX-TFMA-DPA+• with a 46% quantum yield and a τ = 11.5 ± 0.6 ns lifetime. This work demonstrates that the PXX+• D1 electronic excited state can serve as a promising super-oxidant for challenging oxidation reactions relevant to solar-energy applications.