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RESEARCH PRODUCT

Electronic structure and energy decomposition analyses as a tool to interpret the redox potential ranking of naphtho-, biphenyl- and biphenylenequinone isomers

Daniele TomeriniDaniele TomeriniOlivier PolitanoCarlo GattiChristine FrayretChristine Frayret

subject

StereochemistryPopulationRedox potentialsGeneral Physics and Astronomy02 engineering and technologyElectronic structure010402 general chemistry01 natural sciencesRedoxLihium batteriesDFTModellingBiphenylIsomerschemistry.chemical_compoundComputational chemistryPhysical and Theoretical Chemistryeducationeducation.field_of_studyChemistryBiphenyleneAtoms in moleculesAromaticityBiphenylene021001 nanoscience & nanotechnology0104 chemical sciencesQuinoneQuantum Theory of Atoms in MoleculesNaphtoOrganic electrodes0210 nano-technologyAntiaromaticity

description

By calling on modelling approaches we have performed a comparative study on the redox properties of various naphtho-, biphenyl- and biphenylene-quinone isomers. These different compounds exhibit as a whole a redox potential range between 2.09 and 2.90 V vs. Li+/Li. A specific methodology was used to decrypt the interplay among isomerism, aromaticity and antiaromaticity modifications and the stabilization/destabilization effects due to other molecular components on this key electrochemical feature for electrode materials of batteries. In particular, energy decomposition analysis, within the Quantum Theory of Atoms in Molecules, along with the electron and electron spin population changes upon reduction nicely rationalise the observed potential trends. While 1,2- and 2,3-isomers show the highest/lowest redox potential in the biphenylene-quinone series, a reverse trend is observed for the naphtho-quinone, the compound having the two carbonyl groups on distinct rings being characterized by an intermediate value in both cases. There is instead almost no differentiation between 1,2 and 2,3 isomers for the biphenyl-quinone family.

10.1039/c6cp04225bhttps://dx.doi.org/10.1039/c6cp04225b