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Electron donor-acceptor (EDA) complex photochemistry has emerged as a vibrant area in visible-light-mediated synthetic radical chemistry. However, theoretical insights into the reaction mechanisms remain limited. Our study investigates the influence of solvent polarity and halogen atom types on radical reaction pathways in EDA complexes. We demonstrate that solvent polarity modulates the charge transfer and spatial arrangement within EDA complexes, thereby influencing their stability and reaction kinetics. Iodide ions play a crucial role in facilitating free radical generation and stabilizing reaction intermediates. Different halogen atom types exhibit distinct effects on radical reactions. Variations in radical concentration and solvent environment further affect the pathway selectivity. Additionally, light conditions influence the free radical generation and pathway selectivity. Our findings enhance the understanding of EDA complex photochemistry and radical reactions, offering insights for organic synthesis and photochemistry applications.

Mechanistic explorations and kinetic evaluations were performed based on electronic structure calculations at the CASPT2//CASSCF level of theory, the Fermi's golden rule combined with the Dexter model, and the Marcus theory to unveil the key factors regulating the processes of photocatalytic C(sp 3 )-H amidation starting from the newly emerged nitrene precursor of hydroxamates. The highly reactive nitrene was found to be generated efficiently via a triplet-triplet energy transfer process and to be benefited from the advantages of hydroxamates with long-range charge-transfer (CT) excitation from the N-centered lone pair to the 3,5-bis(trifluoromethyl)benzoyl group. The properties of the metal-to-ligand charge-transfer (MLCT) state of photocatalysts, the functionalization of chemical moieties for substrates involved in the charge-transfer (CT) excitation, such as the electron-withdrawing trifluoromethyl group, and the energetic levels of singlet and triplet reaction pathways may regulate the reaction yield of C(sp 3 )-H amidation. Kinetic evaluations show that the triplet-triplet energy transfer is the main driving force of the reaction rather than the single electron transfer process. The effects of electronic coupling, molecular rigidity, and excitation energies on the energy transfer efficiency were further discussed. Finally, we investigated the inverted behavior of single-electron transfer, which is correlated unfavorably to the catalytic efficiency and amidation reaction. All theoretical explorations allow us to better understand the generation of nitrene with visible-light photocatalysts, to expand highly efficient substrate sources, and to broaden our scope of available photosensitizers for various cross-coupling reactions and the construction of N-heterocycles., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Prussian blue analogues (PBAs) have been considered as promising cathodes for aqueous zinc-ion batteries because of their open framework for accommodating large ions, tunable valence state, and facile synthesis. Among PBAs, potassium manganese hexacyanoferrate (KMHCF) is favored due to its high working voltage, high specific capacity, and low cost. However, it suffers from severe capacity decay and poor rate capability, which are mainly a result of poor intrinsic conductivity, irreversible phase transition, transition metal dissolution, and structural collapse during charge/discharge cycling. These issues extremely limit its practical application. In order to solve these problems, conductive polypyrrole (PPy) was used to coat KMHCF microcubes to form KMHCF@PPy composites to achieve superior rate capability and prolonged cycle life. With the PPy coating, the KMHCF@PPy composite delivers a discharge capacity of 107.6 mA h g -1 after 100 cycles at 100 mA g -1 , and even at 500 mA g -1 after 500 cycles, 64.2 mA h g -1 still remained. The excellent electrochemical performance can be attributed to the effects from PPy. On the one hand, PPy supplies an effective electronic transmission network for KMHCF to enhance the electronic conductivity. On the other hand, it plays the role of a protective layer to effectively inhibit the dissolution of Mn and the phase transition during the cycling.

Tris(8-hydroxyquinolinato)aluminum (Alq(3)) has been widely used in organic light-emitting diodes (OLEDs) both as electron transport and light-emitting materials. To gain a deeper understanding for its carrier transport properties, we carry out first-principle band-structure calculations using density-functional theory with generalized gradient approximation by the Becke exchange plus Lee-Yang-Parr correlation functional. The intermolecular interaction related to transport behavior has been analyzed from the Gamma-point wave function as well as from the bandwidths and band gaps. From the calculated bandwidths of the frontier bands as well as the effective masses of the electron and the hole, we conclude that the mobility of electron is about 2-3 times larger than that for the hole. Furthermore, when several bands near Fermi surface are taken into account, we find that the interband gaps within the unoccupied bands are generally smaller than those for the occupied bands, which indicate that the electron can hop from one band to another, much easier than the hole, through electron-phonon coupling for instance, thus, effectively representing an even larger mobility for the electron than for the hole. Therefore, from both the intra-band and inter-band processes point of view, the theory shows that that Alq(3) is a good electron transport material.