[{"abstract":[{"text":"Several problems arise at the O2 (positive) electrode in the Li-air battery, including solvent/electrode decomposition and electrode passivation by insulating Li2O2. Progress partially depends on exploring the basic electrochemistry of O2 reduction. Here we describe the effect of complexing-cations on the electrochemical reduction of O2 in DMSO in the presence and absence of a Li salt. The solubility of alkaline peroxides in DMSO is enhanced by the complexing-cations, consistent with their strong interaction with reduced O2. The complexing-cations also increase the rate of the 1-electron O2 reduction to O2•– by up to six-fold (k° = 2.4 ×10–3 to 1.5 × 10–2 cm s–1) whether or not Li+ ions are present. In the absence of Li+, the complexing-cations also promote the reduction of O2•– to O22–. In the presence of Li+ and complexing-cations, and despite the interaction of the reduced O2 with the latter, SERS confirms that the product is still Li2O2.","lang":"eng"}],"doi":"10.1021/jp4093805","publication_identifier":{"issn":["1932-7447","1932-7455"]},"day":"29","date_published":"2014-01-29T00:00:00Z","type":"journal_article","date_updated":"2021-01-12T08:12:53Z","year":"2014","citation":{"ieee":"C. Li <i>et al.</i>, “Aprotic Li–O2 battery: Influence of complexing agents on oxygen reduction in an aprotic solvent,” <i>The Journal of Physical Chemistry C</i>, vol. 118, no. 7. ACS, pp. 3393–3401, 2014.","chicago":"Li, Chunmei, Olivier Fontaine, Stefan Alexander Freunberger, Lee Johnson, Sylvie Grugeon, Stéphane Laruelle, Peter G. Bruce, and Michel Armand. “Aprotic Li–O2 Battery: Influence of Complexing Agents on Oxygen Reduction in an Aprotic Solvent.” <i>The Journal of Physical Chemistry C</i>. ACS, 2014. <a href=\"https://doi.org/10.1021/jp4093805\">https://doi.org/10.1021/jp4093805</a>.","apa":"Li, C., Fontaine, O., Freunberger, S. A., Johnson, L., Grugeon, S., Laruelle, S., … Armand, M. (2014). Aprotic Li–O2 battery: Influence of complexing agents on oxygen reduction in an aprotic solvent. <i>The Journal of Physical Chemistry C</i>. ACS. <a href=\"https://doi.org/10.1021/jp4093805\">https://doi.org/10.1021/jp4093805</a>","ama":"Li C, Fontaine O, Freunberger SA, et al. Aprotic Li–O2 battery: Influence of complexing agents on oxygen reduction in an aprotic solvent. <i>The Journal of Physical Chemistry C</i>. 2014;118(7):3393-3401. doi:<a href=\"https://doi.org/10.1021/jp4093805\">10.1021/jp4093805</a>","ista":"Li C, Fontaine O, Freunberger SA, Johnson L, Grugeon S, Laruelle S, Bruce PG, Armand M. 2014. Aprotic Li–O2 battery: Influence of complexing agents on oxygen reduction in an aprotic solvent. The Journal of Physical Chemistry C. 118(7), 3393–3401.","mla":"Li, Chunmei, et al. “Aprotic Li–O2 Battery: Influence of Complexing Agents on Oxygen Reduction in an Aprotic Solvent.” <i>The Journal of Physical Chemistry C</i>, vol. 118, no. 7, ACS, 2014, pp. 3393–401, doi:<a href=\"https://doi.org/10.1021/jp4093805\">10.1021/jp4093805</a>.","short":"C. Li, O. Fontaine, S.A. Freunberger, L. Johnson, S. Grugeon, S. Laruelle, P.G. Bruce, M. Armand, The Journal of Physical Chemistry C 118 (2014) 3393–3401."},"extern":"1","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","status":"public","volume":118,"title":"Aprotic Li–O2 battery: Influence of complexing agents on oxygen reduction in an aprotic solvent","month":"01","intvolume":"       118","publication_status":"published","oa_version":"None","date_created":"2020-01-15T12:17:28Z","article_processing_charge":"No","author":[{"full_name":"Li, Chunmei","first_name":"Chunmei","last_name":"Li"},{"last_name":"Fontaine","first_name":"Olivier","full_name":"Fontaine, Olivier"},{"full_name":"Freunberger, Stefan Alexander","orcid":"0000-0003-2902-5319","last_name":"Freunberger","first_name":"Stefan Alexander","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425"},{"full_name":"Johnson, Lee","first_name":"Lee","last_name":"Johnson"},{"full_name":"Grugeon, Sylvie","first_name":"Sylvie","last_name":"Grugeon"},{"last_name":"Laruelle","first_name":"Stéphane","full_name":"Laruelle, Stéphane"},{"full_name":"Bruce, Peter G.","last_name":"Bruce","first_name":"Peter G."},{"last_name":"Armand","first_name":"Michel","full_name":"Armand, Michel"}],"issue":"7","publication":"The Journal of Physical Chemistry C","_id":"7301","article_type":"original","publisher":"ACS","language":[{"iso":"eng"}],"page":"3393-3401","quality_controlled":"1"},{"date_updated":"2021-01-12T08:07:17Z","citation":{"ieee":"T.-C. Lin <i>et al.</i>, “Molecular origins of the high-performance nonlinear optical susceptibility in a phenolic polyene chromophore: Electron density distributions, hydrogen bonding, and ab initio calculations,” <i>The Journal of Physical Chemistry C</i>, vol. 117, no. 18. American Chemical Society (ACS), pp. 9416–9430, 2013.","chicago":"Lin, Tze-Chia, Jacqueline M. Cole, Andrew P Higginbotham, Alison J. Edwards, Ross O. Piltz, Javier Pérez-Moreno, Ji-Youn Seo, Seung-Chul Lee, Koen Clays, and O-Pil Kwon. “Molecular Origins of the High-Performance Nonlinear Optical Susceptibility in a Phenolic Polyene Chromophore: Electron Density Distributions, Hydrogen Bonding, and Ab Initio Calculations.” <i>The Journal of Physical Chemistry C</i>. American Chemical Society (ACS), 2013. <a href=\"https://doi.org/10.1021/jp400648q\">https://doi.org/10.1021/jp400648q</a>.","apa":"Lin, T.-C., Cole, J. M., Higginbotham, A. P., Edwards, A. J., Piltz, R. O., Pérez-Moreno, J., … Kwon, O.-P. (2013). Molecular origins of the high-performance nonlinear optical susceptibility in a phenolic polyene chromophore: Electron density distributions, hydrogen bonding, and ab initio calculations. <i>The Journal of Physical Chemistry C</i>. American Chemical Society (ACS). <a href=\"https://doi.org/10.1021/jp400648q\">https://doi.org/10.1021/jp400648q</a>","ama":"Lin T-C, Cole JM, Higginbotham AP, et al. Molecular origins of the high-performance nonlinear optical susceptibility in a phenolic polyene chromophore: Electron density distributions, hydrogen bonding, and ab initio calculations. <i>The Journal of Physical Chemistry C</i>. 2013;117(18):9416-9430. doi:<a href=\"https://doi.org/10.1021/jp400648q\">10.1021/jp400648q</a>","ista":"Lin T-C, Cole JM, Higginbotham AP, Edwards AJ, Piltz RO, Pérez-Moreno J, Seo J-Y, Lee S-C, Clays K, Kwon O-P. 2013. Molecular origins of the high-performance nonlinear optical susceptibility in a phenolic polyene chromophore: Electron density distributions, hydrogen bonding, and ab initio calculations. The Journal of Physical Chemistry C. 117(18), 9416–9430.","mla":"Lin, Tze-Chia, et al. “Molecular Origins of the High-Performance Nonlinear Optical Susceptibility in a Phenolic Polyene Chromophore: Electron Density Distributions, Hydrogen Bonding, and Ab Initio Calculations.” <i>The Journal of Physical Chemistry C</i>, vol. 117, no. 18, American Chemical Society (ACS), 2013, pp. 9416–30, doi:<a href=\"https://doi.org/10.1021/jp400648q\">10.1021/jp400648q</a>.","short":"T.-C. Lin, J.M. Cole, A.P. Higginbotham, A.J. Edwards, R.O. Piltz, J. Pérez-Moreno, J.-Y. Seo, S.-C. Lee, K. Clays, O.-P. Kwon, The Journal of Physical Chemistry C 117 (2013) 9416–9430."},"year":"2013","date_published":"2013-05-09T00:00:00Z","type":"journal_article","doi":"10.1021/jp400648q","day":"09","publication_identifier":{"issn":["1932-7447","1932-7455"]},"abstract":[{"text":"The molecular and supramolecular origins of the superior nonlinear optical (NLO) properties observed in the organic phenolic triene material, OH1 (2-(3-(4-hydroxystyryl)-5,5-dimethylcyclohex-2-enylidene)malononitrile), are presented. The molecular charge-transfer distribution is topographically mapped, demonstrating that a uniformly delocalized passive electronic medium facilitates the charge-transfer between the phenolic electron donor and the cyano electron acceptors which lie at opposite ends of the molecule. Its ability to act as a “push–pull” π-conjugated molecule is quantified, relative to similar materials, by supporting empirical calculations; these include bond-length alternation and harmonic-oscillator stabilization energy (HOSE) tests. Such tests, together with frontier molecular orbital considerations, reveal that OH1 can exist readily in its aromatic (neutral) or quinoidal (charge-separated) state, thereby overcoming the “nonlinearity-thermal stability trade-off”. The HOSE calculation also reveals a correlation between the quinoidal resonance contribution to the overall structure of OH1 and the UV–vis absorption peak wavelength in the wider family of configurationally locked polyene framework materials. Solid-state tensorial coefficients of the molecular dipole, polarizability, and the first hyperpolarizability for OH1 are derived from the first-, second-, and third-order electronic moments of the experimental charge-density distribution. The overall solid-state molecular dipole moment is compared with those from gas-phase calculations, revealing that crystal field effects are very significant in OH1. The solid-state hyperpolarizability derived from this charge-density study affords good agreement with gas-phase calculations as well as optical measurements based on hyper-Rayleigh scattering (HRS) and electric-field-induced second harmonic (EFISH) generation. This lends support to the further use of charge-density studies to calculate solid-state hyperpolarizability coefficients in other organic NLO materials. Finally, this charge-density study is also employed to provide an advanced classification of hydrogen bonds in OH1, which requires more stringent criteria than those from conventional structure analysis. As a result, only the strongest OH···NC interaction is so classified as a true hydrogen bond. Indeed, it is this electrostatic interaction that influences the molecular charge transfer: the other four, weaker, nonbonded contacts nonetheless affect the crystal packing. Overall, the establishment of these structure–property relationships lays a blueprint for designing further, more NLO efficient, materials in this industrially leading organic family of compounds.","lang":"eng"}],"volume":117,"extern":"1","user_id":"3E5EF7F0-F248-11E8-B48F-1D18A9856A87","status":"public","publication":"The Journal of Physical Chemistry C","_id":"6370","author":[{"full_name":"Lin, Tze-Chia","last_name":"Lin","first_name":"Tze-Chia"},{"full_name":"Cole, Jacqueline M.","last_name":"Cole","first_name":"Jacqueline M."},{"orcid":"0000-0003-2607-2363","full_name":"Higginbotham, Andrew P","first_name":"Andrew P","last_name":"Higginbotham","id":"4AD6785A-F248-11E8-B48F-1D18A9856A87"},{"full_name":"Edwards, Alison J.","first_name":"Alison J.","last_name":"Edwards"},{"full_name":"Piltz, Ross O.","last_name":"Piltz","first_name":"Ross O."},{"full_name":"Pérez-Moreno, Javier","first_name":"Javier","last_name":"Pérez-Moreno"},{"first_name":"Ji-Youn","last_name":"Seo","full_name":"Seo, Ji-Youn"},{"full_name":"Lee, Seung-Chul","last_name":"Lee","first_name":"Seung-Chul"},{"first_name":"Koen","last_name":"Clays","full_name":"Clays, Koen"},{"first_name":"O-Pil","last_name":"Kwon","full_name":"Kwon, O-Pil"}],"issue":"18","publication_status":"published","oa_version":"None","date_created":"2019-05-03T09:40:31Z","title":"Molecular origins of the high-performance nonlinear optical susceptibility in a phenolic polyene chromophore: Electron density distributions, hydrogen bonding, and ab initio calculations","month":"05","intvolume":"       117","page":"9416-9430","quality_controlled":"1","language":[{"iso":"eng"}],"publisher":"American Chemical Society (ACS)"}]