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Organic electrode materials offer unique opportunities to utilize ion-electrode interactions to develop diverse, versatile, and high-performing secondary batteries, particularly for applications requiring high power densities. However, a lack of well-defined structure–property relationships for redox-active organic materials restricts the advancement of the field. Herein, we investigate a family of diimide-based polymer materials with several charge-compensating ions (Li + , Na + , K + ) in order to systematically probe how redox-active moiety, ion, and polymer flexibility dictate their thermodynamic and kinetic properties. When favorable ion-electrode interactions are employed ( e.g. , soft K + anions with soft perylenediimide dianions), the resulting batteries demonstrate increased working potentials and improved cycling stabilities. Further, for all polymers examined herein, we demonstrate that K + accesses the highest percentage of redox-active groups due to its small solvation shell/energy. Through crown ether experiments, cyclic voltammetry, and activation energy measurements, we provide insights into the charge compensation mechanisms of three different polymer structures and rationalize these findings in terms of the differing degrees of improvements observed when cycling with K + . Critically, we find that the most flexible polymer enables access to the highest fraction of active sites due to the small activation energy barrier during charge/discharge. These results suggest that improved capacities may be accessible by employing more flexible structures. Overall, our in-depth structure–activity investigation demonstrates how variables such as polymer structure and cation can be used to optimize battery performance and enable the realization of novel battery chemistries. 

Single‐electron transfer (SET) plays a critical role in many chemical processes, from organic synthesis to environmental remediation. However, the selective reduction of inert substrates (E_p/2<−2 V vs Fc/Fc⁺), such as ubiquitous electron‐neutral and electron‐rich (hetero)aryl chlorides, remains a major challenge. Current approaches largely rely on catalyst photoexcitation to reach the necessary deeply reducing potentials or suffer from limited substrate scopes. Herein, we demonstrate that cumulenes–organic molecules with multiple consecutive double bonds–can function as catalytic redox mediators for the electroreductive radical borylation of (hetero)aryl chlorides at relatively mild cathodic potentials (approximately −1.9 V vs. Ag/AgCl) without the need for photoirradiation. Electrochemical, spectroscopic, and computational studies support that step‐wise electron transfer from reduced cumulenes to electron‐neutral chloroarenes is followed by thermodynamically favorable mesolytic cleavage of the aryl radical anion to generate the desired aryl radical intermediate. Our findings will guide the development of other sustainable, purely electroreductive radical transformations of inert molecules using organic redox mediators.

 

Single‐electron transfer (SET) plays a critical role in many chemical processes, from organic synthesis to environmental remediation. However, the selective reduction of inert substrates (E_p/2<−2 V vs Fc/Fc⁺), such as ubiquitous electron‐neutral and electron‐rich (hetero)aryl chlorides, remains a major challenge. Current approaches largely rely on catalyst photoexcitation to reach the necessary deeply reducing potentials or suffer from limited substrate scopes. Herein, we demonstrate that cumulenes–organic molecules with multiple consecutive double bonds–can function as catalytic redox mediators for the electroreductive radical borylation of (hetero)aryl chlorides at relatively mild cathodic potentials (approximately −1.9 V vs. Ag/AgCl) without the need for photoirradiation. Electrochemical, spectroscopic, and computational studies support that step‐wise electron transfer from reduced cumulenes to electron‐neutral chloroarenes is followed by thermodynamically favorable mesolytic cleavage of the aryl radical anion to generate the desired aryl radical intermediate. Our findings will guide the development of other sustainable, purely electroreductive radical transformations of inert molecules using organic redox mediators.

 

Hydrogen sulfide (H 2 S) is an endogenous gasotransmitter with potential therapeutic value for treating a range of disorders, such as ischemia-reperfusion injury resulting from a myocardial infarction or stroke. However, the medicinal delivery of H 2 S is hindered by its corrosive and toxic nature. In addition, small molecule H 2 S donors often generate other reactive and sulfur-containing species upon H 2 S release, leading to unwanted side effects. Here, we demonstrate that H 2 S release from biocompatible porous solids, namely metal–organic frameworks (MOFs), is a promising alternative strategy for H 2 S delivery under physiologically relevant conditions. In particular, through gas adsorption measurements and density functional theory calculations we establish that H 2 S binds strongly and reversibly within the tetrahedral pockets of the fumaric acid-derived framework MOF-801 and the mesaconic acid-derived framework Zr-mes, as well as the new itaconic acid-derived framework CORN-MOF-2. These features make all three frameworks among the best materials identified to date for the capture, storage, and delivery of H 2 S. In addition, these frameworks are non-toxic to HeLa cells and capable of releasing H 2 S under aqueous conditions, as confirmed by fluorescence assays. Last, a cellular ischemia-reperfusion injury model using H9c2 rat cardiomyoblast cells corroborates that H 2 S-loaded MOF-801 is capable of mitigating hypoxia-reoxygenation injury, likely due to the release of H 2 S. Overall, our findings suggest that H 2 S-loaded MOFs represent a new family of easily-handled solid sources of H 2 S that merit further investigation as therapeutic agents. In addition, our findings add Zr-mes and CORN-MOF-2 to the growing lexicon of biocompatible MOFs suitable for drug delivery. 

In this study, high‐performance ionic soft actuators are developed for the first time using collectively exhaustive boron and sulfur co‐doped porous carbon electrodes (BS‐COF‐Cs), derived from thiophene‐based boronate‐linked covalent organic framework (T‐COF) as a template. The one‐electron deficiency of boron compared to carbon leads to the generation of hole charge carriers, while sulfur, owing to its high electron density, creates electron carriers in BS‐COF‐C electrodes. This antagonistic functionality of BS‐COF‐C electrodes assists the charge‐transfer rate, leading to fast charge separation in the developed ionic soft actuator under alternating current input signals. Furthermore, the hierarchical porosity, high surface area, and synergistic effect of co‐doping of the BS‐COF‐Cs play crucial roles in offering effective interaction of BS‐COF‐Cs with poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), leading to the generation of high electro‐chemo‐mechanical performance of the corresponding composite electrodes. Finally, the developed ionic soft actuator based on the BS‐COF‐C electrode exhibits large bending strain (0.62%), excellent durability (90% retention for 6 hours under operation), and 2.7 times higher bending displacement than PEDOT:PSS under extremely low harmonic input of 0.5 V. This study reveals that the antagonistic functionality of heteroatom co‐doped electrodes plays a crucial role in accelerating the actuation performance of ionic artificial muscles.