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Full-Text Articles in Chemistry

Dications Of Benzylidenefluorene And Diphenylmethylidene Fluorene: The Relationship Between Magnetic And Energetic Measures Of Antiaromaticity, Catherine Do, Julianne Hatfield, Shirali Patel, D Vasudevan, Cornelia Tirla, Nancy S. Mills Jan 2011

Dications Of Benzylidenefluorene And Diphenylmethylidene Fluorene: The Relationship Between Magnetic And Energetic Measures Of Antiaromaticity, Catherine Do, Julianne Hatfield, Shirali Patel, D Vasudevan, Cornelia Tirla, Nancy S. Mills

Chemistry Faculty Research

Oxidation of m- and p-substituted benzylidene fluorenes to antiaromatic dications was attempted by electrochemical and chemical means. Electrochemical oxidation to dications was successful for benzylidene fluorenes with p-methoxy, p-methyl, p-fluoro, and unsubstituted phenyl rings in the 3-position; attempts to oxidize the m-substituted derivatives via electrochemistry were unsuccessful. Chemical oxidation with SbF5/SO2ClF gave the dication of 9-[(4-methoxyphenyl)methylene]-9H-fluorene cleanly; oxidation of all other substituted benzylidene fluorenes resulted in mixtures of products. The excellent linear relationship between the chemical shifts calculated by the GIAO method and the experimental shifts for the p-methoxy-substituted benzylidene fluorene dication …


Diffuse-Charge Dynamics Of Ionic Liquids In Electrochemical Systems, Hui Zhao Jan 2011

Diffuse-Charge Dynamics Of Ionic Liquids In Electrochemical Systems, Hui Zhao

Mechanical Engineering Faculty Research

We employ a continuum theory of solvent-free ionic liquids accounting for both short-range electrostatic correlations and steric effects (finite ion size) [Bazant et al., Phys. Rev. Lett. 106, 046102 (2011)] to study the response of a model microelectrochemical cell to a step voltage. The model problem consists of a 1-1 symmetric ionic liquid between two parallel blocking electrodes, neglecting any transverse transport phenomena. Matched asymptotic expansions in the limit of thin double layers are applied to analyze the resulting one-dimensional equations and study the overall charge-time relation in the weakly nonlinear regime. One important conclusion is that our …