Reaction generality is crucial in determining the overall impact and usefulness of synthetic methods. Typical generalization protocols require a priori mechanistic understanding and suffer when applied to complex, less understood systems. We developed an additive mapping approach that rapidly expands the utility of synthetic methods while generating concurrent mechanistic insight. Validation of this approach on the metallaphotoredox decarboxylative arylation resulted in the discovery of a phthalimide ligand additive that overcomes many lingering limitations of this reaction and has important mechanistic implications for nickel-catalyzed cross-couplings.

The incorporation of a hexadecyl group on imidazolium, pyridinium, and pyrrolidinium scaffolds produces low-molecular-weight ionic organogelators that can gel several types of ionic liquids, deep eutectic solvents (DESs), and several molecular organic solvents. Minimum gelator concentrations fall in the 0.9–15.0% (w/v) range, with the lower end of the gelator concentrations observed in the gelation of DESs. On the basis of polarized optical microscopy, differential scanning calorimetry, and X-ray data, crystallization of these salts appear to produce high-surface-area crystals, which generate sufficiently stable three-dimensional networks that are capable of trapping the solvent molecules. Importantly, the nature of the fluid component of the gel appears to have a profound effect on the morphology of the crystallized organogelators. On the other hand, the organogelators appeared to modulate phase transitions of the liquids.

Reaction generality is crucial in determining the overall impact and usefulness of organic synthetic methods. In contrast, contemporary generalization processes seem unable to meet the growing demand for robust methodology. We sought to develop an accelerated approach towards achieving generality, inspired by phenotypic screening, that rapidly expands the scope and utility of synthetic methods. This approach was validated by example of the metallaphotoredox decarboxylative arylation, resulting in the discovery of a novel additive that overcomes many lingering limitations of this method and has significant mechanistic implications for nickel-catalyzed cross couplings in general.

An organic diode is demonstrated that near‐field energy transfers to molecules in solution via surface plasmon polaritons, in contrast to typical far‐field excitation via absorption of traveling photons. Electrically generated excitons couple to surface plasmon modes in the cathode; the plasmons subsequently excite chromophore molecules on top of the cathode. External quantum efficiency and time resolved photoluminescence measurements are used to characterize the diode and the near‐field energy transfer process. In addition, it is shown that excited chromophores can charge‐transfer to quencher molecules, illustrating the potential of this device to be used for photochemical applications.

Reaction generality is crucial in determining the overall impact and usefulness of organic synthetic methods. In contrast, contemporary generalization processes seem unable to meet the growing demand for robust methodology. We sought to develop an accelerated approach towards achieving generality, inspired by phenotypic screening, that rapidly expands the scope and utility of synthetic methods. This approach was validated by example of the metallaphotoredox decarboxylative arylation, resulting in the discovery of a novel additive that overcomes many lingering limitations of this method and has significant mechanistic implications for nickel-catalyzed cross couplings in general.