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2.
ACS Appl Mater Interfaces ; 13(6): 7135-7141, 2021 Feb 17.
Article in English | MEDLINE | ID: mdl-33543926

ABSTRACT

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.

3.
Angew Chem Int Ed Engl ; 60(8): 3989-3993, 2021 02 19.
Article in English | MEDLINE | ID: mdl-33179414

ABSTRACT

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.


Subject(s)
Alkenes/chemistry , Copper/chemistry , Cyclobutanes/chemistry , Light , Catalysis , Cations/chemistry , Cycloaddition Reaction , Cyclobutanes/chemical synthesis , Stereoisomerism
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