Understanding
the properties that govern the kinetics of charge
storage will enable informed design strategies and improve the rate
performance of future battery materials. Herein, we study the effects
of structural ordering in organic electrode materials on their charge
storage mechanisms. A redox active unit, N,N′-diphenyl-phenazine, was incorporated into three
materials which exhibited varying degrees of ordering. From cyclic
voltammetry analysis, the crystalline small molecule exhibited diffusion-limited
behavior, likely arising from structural rearrangements that occur
during charge/discharge. Conversely, a branched polymer network displayed
surface-controlled kinetics, attributed to the amorphous structure
which enabled fast ionic transport throughout charge/discharge, unimpeded
by sluggish structural rearrangements. These results suggest a method
for designing new materials for battery electrodes with battery-like
energy densities and pseudocapacitor-like rate capabilities.
The sole method available for the photocycloaddition of unconjugated aliphatic alkenes is the Cu‐catalyzed Salomon–Kochi reaction. The [Cu(OTf)]2⋅benzene catalyst that has been standard in this reaction for many decades, however, is air‐sensitive, prone to photodecomposition, and poorly reactive towards sterically bulky alkene substrates. Using bench‐stable precursors, an improved catalyst system with superior reactivity and photostability has been designed, and it offers significantly expanded substrate scope. The utility of this new catalyst for the preparation of sterically crowded cyclobutane structures is highlighted through the preparation of the cores of the natural products sulcatine G and perforatol.
The sole method available for the photocycloaddition of unconjugated aliphatic alkenes is the Cu‐catalyzed Salomon–Kochi reaction. The [Cu(OTf)]2⋅benzene catalyst that has been standard in this reaction for many decades, however, is air‐sensitive, prone to photodecomposition, and poorly reactive towards sterically bulky alkene substrates. Using bench‐stable precursors, an improved catalyst system with superior reactivity and photostability has been designed, and it offers significantly expanded substrate scope. The utility of this new catalyst for the preparation of sterically crowded cyclobutane structures is highlighted through the preparation of the cores of the natural products sulcatine G and perforatol.
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