On the Tunability of Toxicity for Viologen-Derivatives as Anolyte for Neutral Aqueous Organic Redox Flow Batteries.

Viologen-derivatives are the most widely used redox organic molecules for neutral pH negative electrolyte of redox flow batteries. However, the long-established toxicity of the herbicide methyl-viologen raises concern for deployment of viologen-derivatives at large scale in flow batteries. Herein, we demonstrate the radically different cytotoxicity and toxicology of a series of viologen-derivatives in in vitro assays using model organisms representative of human and environmental exposure, namely human lung carcinoma epithelial cell line (A549) and the yeast Saccharomyces cerevisiae. The results show that safe viologen derivatives can be molecularly engineered, representing a promising family of negolyte materials for neutral redox flow batteries.

Synthesis of 1,4-ketoaldehydes and 1,4-diketones by Mo-catalyzed oxidative cleavage of cyclobutane-1,2-diols.

A new two-step procedure for the synthesis of 1,4-dicarbonyls has been developed involving an efficient and clean Mo-catalyzed oxidative cleavage of cyclobutane-1,2-diols with DMSO, which is used as solvent and oxidant. The required starting glycols were prepared by nucleophilic additions of organolithiums and Grignard reagents to easily available 2-hydroxycyclobutanones.

Addressing Practical Use of Viologen-Derivatives in Redox Flow Batteries through Molecular Engineering.

In practical scenarios, viologen-derivatives face an accelerated degradation in the unavoidable presence of traces of oxygen in large-scale redox flow batteries. Herein, we confirm the primary degradation mechanism and propose a straightforward, cheap, and fast method to evaluate the stability of viologen-derivatives toward this degradation. Considering that the cleavage of the N-substituent is the main proposed pathway for viologen degradation, a new viologen-derivative, bearing an alkylsulfonate chain with a secondary carbon center joined to the N atom, is synthesized to illustrate how molecular engineering can be used to improve stability.

Mo-Catalyzed One-Pot Synthesis of N-Polyheterocycles from Nitroarenes and Glycols with Recycling of the Waste Reduction Byproduct. Substituent-Tuned Photophysical Properties.

A catalytic domino reduction-imine formation-intramolecular cyclization-oxidation for the general synthesis of a wide variety of biologically relevant N-polyheterocycles, such as quinoxaline- and quinoline-fused derivatives, and phenanthridines, is reported. A simple, easily available, and environmentally friendly dioxomolybdenum(VI) complex has proven to be a highly efficient and versatile catalyst for transforming a broad range of starting nitroarenes involving several redox processes. Not only is this a sustainable, step-economical as well as air- and moisture-tolerant method, but also it is worth highlighting that the waste byproduct generated in the first step of the sequence is recycled and incorporated in the final target molecule, improving the overall synthetic efficiency. Moreover, selected indoloquinoxalines have been photophysically characterized in cyclohexane and toluene with exceptional fluorescence quantum yields above 0.7 for the alkyl derivatives.

Generation of alkoxysulfonyl radicals from chlorosulfates and their intramolecular capture with alkynes to obtain sultones.

An unprecedented radical-mediated reaction of alkyne-containing chlorosulfates to synthesize sultones has been established. The reaction leads to the formation and subsequent capture of alkoxysulfonyl radicals, which are species known for a long time but not studied for synthetic purposes.

Synthesis of Spirocyclic Compounds by a Ring-Expansion/Cationic Cyclization Cascade Reaction of Chlorosulfate Derivatives.

A novel cascade reaction to prepare spirocarbocyclic compounds from chlorosulfate derivatives has been developed. The process involves an unusual thermal elimination of the chlorosulfate moiety, a ring-expansion reaction, and a subsequent cationic cyclization reaction. Despite the relatively complex skeletal rearrangement, the reaction described here is featured by its operational simplicity, being just a thermal process that does not require additional reagents, catalysts, or additives.

Molybdenum-Catalyzed Synthesis of Nitrogenated Polyheterocycles from Nitroarenes and Glycols with Reuse of Waste Reduction Byproduct.

A novel domino reduction/imine formation/intramolecular cyclization/oxidation for the efficient synthesis of pyrrolo(indolo)[1,2-a]quinoxalines and pyrrolo(indolo)[3,2-c]-quinolines from readily available nitrobenzenes and glycols is reported. The process utilizes the carbonyl byproduct of the initial dioxomolybdenum(VI)-catalyzed reduction of nitroaromatics with glycols as a reagent for the imine generation. This method represents the first sustainable domino reaction for the preparation of biologically relevant heterocycles that internally incorporates the waste formed in the first step to the final product.