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Full-Text Articles in Physical Sciences and Mathematics
Does Koopmans’ Paradigm For 1-Electron Oxidation Always Hold? Breakdown Of Ip/EOx Relationship For P-Hydroquinone Ethers And The Role Of Methoxy Group Rotation, Marat R. Talipov, Anitha Boddeda, Sergey V. Lindeman, Rajendra Rathore
Does Koopmans’ Paradigm For 1-Electron Oxidation Always Hold? Breakdown Of Ip/EOx Relationship For P-Hydroquinone Ethers And The Role Of Methoxy Group Rotation, Marat R. Talipov, Anitha Boddeda, Sergey V. Lindeman, Rajendra Rathore
Chemistry Faculty Research and Publications
Koopmans’ paradigm states that electron loss occurs from HOMO, thus forming the basis for the observed linear relationships between HOMO/IP, HOMO/Eox, and IP/Eox. In cases where a molecule undergoes dramatic structural reorganization upon 1-electron oxidation, the IP/Eoxrelationship does not hold, and the origin of which is not understood. For example, X-ray crystallography of the neutral and cation radicals of bicyclo[2.2.1]heptane-annulated p-hydroquinone ethers (THE and MHE) showed that they undergo electron-transfer-induced conformational reorganization and show breakdown of the IP/Eox relationship. DFT calculations revealed that Koopmans’ paradigm …