Interrogation of 2,2′-Bipyrimidines as Low-Potential Two-Electron Electrolytes
- 7 January 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 143 (2), 992-1004
- https://doi.org/10.1021/jacs.0c11267
Abstract
As utilization of renewable energy sources continues to expand, the need for new grid energy storage technologies such as redox flow batteries (RFBs) will be vital. Ultimately, the energy density of a RFB will be dependent on the redox potentials of the respective electrolytes, their solubility, and the number of electrons stored per molecule. With prior literature reports demonstrating the propensity of nitrogen-containing heterocycles to undergo multielectron reduction at low potentials, we focused on the development of a novel electrolyte scaffold based upon a 2,2′-bipyrimidine skeleton. This scaffold is capable of storing two electrons per molecule while also exhibiting a low (∼−2.0 V vs Fc/Fc+) reduction potential. A library of 24 potential bipyrimidine anolytes were synthesized and systematically evaluated to unveil structure–function relationships through computational evaluation. Through analysis of these relationships, it was unveiled that steric interactions disrupting the planarity of the system in the reduced state could be responsible for higher levels of degradation in certain anolytes. The major decomposition pathway was ultimately determined to be protonation of the dianion by solvent, which could be reversed by electrochemical or chemical oxidation. To validate the hypothesis of strain-induced decomposition, two new electrolytes with minimal steric encumbrance were synthesized, evaluated, and found to indeed exhibit higher stability than their sterically hindered counterparts.Funding Information
- National Institute of General Medical Sciences (F32 GM129980)
- Argonne National Laboratory (JCESR)
This publication has 57 references indexed in Scilit:
- Electricity storage for intermittent renewable sourcesEnergy & Environmental Science, 2012
- Large-scale integration of wind power into the existing Chinese energy systemEnergy, 2011
- Development of the all-vanadium redox flow battery for energy storage: a review of technological, financial and policy aspectsInternational Journal of Energy Research, 2011
- Oxidative Dehydrogenation of Dihydropyrimidinones and DihydropyrimidinesOrganic Letters, 2005
- Energies, structures, and electronic properties of molecules in solution with the C‐PCM solvation modelJournal of Computational Chemistry, 2003
- Iron(III)-Catalyzed Synthesis of Dihydropyrimidinones. Improved Conditions for the Biginelli ReactionSynlett, 2000
- A facile halogenation of some hydroxyheterocycles using triphenylphosphine and N-halosuccinimideTetrahedron Letters, 1999
- Chemical Redox Agents for Organometallic ChemistryChemical Reviews, 1996
- Metal-to-ligand charge-transfer (MLCT) photochemistry: experimental evidence for the participation of a higher lying MLCT state in polypyridyl complexes of ruthenium(II) and osmium(II)The Journal of Physical Chemistry, 1990
- Solvent dependence of metal-to-ligand charge-transfer transitions. Evidence for initial electron localization in MLCT excited states of 2,2'-bipyridine complexes of ruthenium(II) and osmium(II)Inorganic Chemistry, 1984