--- _id: '7301' abstract: - lang: eng 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. article_processing_charge: No article_type: original author: - first_name: Chunmei full_name: Li, Chunmei last_name: Li - first_name: Olivier full_name: Fontaine, Olivier last_name: Fontaine - first_name: Stefan Alexander full_name: Freunberger, Stefan Alexander id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425 last_name: Freunberger orcid: 0000-0003-2902-5319 - first_name: Lee full_name: Johnson, Lee last_name: Johnson - first_name: Sylvie full_name: Grugeon, Sylvie last_name: Grugeon - first_name: Stéphane full_name: Laruelle, Stéphane last_name: Laruelle - first_name: Peter G. full_name: Bruce, Peter G. last_name: Bruce - first_name: Michel full_name: Armand, Michel last_name: Armand citation: ama: 'Li C, Fontaine O, Freunberger SA, et al. Aprotic Li–O2 battery: Influence of complexing agents on oxygen reduction in an aprotic solvent. The Journal of Physical Chemistry C. 2014;118(7):3393-3401. doi:10.1021/jp4093805' 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. The Journal of Physical Chemistry C. ACS. https://doi.org/10.1021/jp4093805' 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.” The Journal of Physical Chemistry C. ACS, 2014. https://doi.org/10.1021/jp4093805.' ieee: 'C. Li et al., “Aprotic Li–O2 battery: Influence of complexing agents on oxygen reduction in an aprotic solvent,” The Journal of Physical Chemistry C, vol. 118, no. 7. ACS, pp. 3393–3401, 2014.' 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.” The Journal of Physical Chemistry C, vol. 118, no. 7, ACS, 2014, pp. 3393–401, doi:10.1021/jp4093805.' 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. date_created: 2020-01-15T12:17:28Z date_published: 2014-01-29T00:00:00Z date_updated: 2021-01-12T08:12:53Z day: '29' doi: 10.1021/jp4093805 extern: '1' intvolume: ' 118' issue: '7' language: - iso: eng month: '01' oa_version: None page: 3393-3401 publication: The Journal of Physical Chemistry C publication_identifier: issn: - 1932-7447 - 1932-7455 publication_status: published publisher: ACS quality_controlled: '1' status: public title: 'Aprotic Li–O2 battery: Influence of complexing agents on oxygen reduction in an aprotic solvent' type: journal_article user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87 volume: 118 year: '2014' ... --- _id: '6370' abstract: - lang: eng 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.' author: - first_name: Tze-Chia full_name: Lin, Tze-Chia last_name: Lin - first_name: Jacqueline M. full_name: Cole, Jacqueline M. last_name: Cole - first_name: Andrew P full_name: Higginbotham, Andrew P id: 4AD6785A-F248-11E8-B48F-1D18A9856A87 last_name: Higginbotham orcid: 0000-0003-2607-2363 - first_name: Alison J. full_name: Edwards, Alison J. last_name: Edwards - first_name: Ross O. full_name: Piltz, Ross O. last_name: Piltz - first_name: Javier full_name: Pérez-Moreno, Javier last_name: Pérez-Moreno - first_name: Ji-Youn full_name: Seo, Ji-Youn last_name: Seo - first_name: Seung-Chul full_name: Lee, Seung-Chul last_name: Lee - first_name: Koen full_name: Clays, Koen last_name: Clays - first_name: O-Pil full_name: Kwon, O-Pil last_name: Kwon citation: 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. The Journal of Physical Chemistry C. 2013;117(18):9416-9430. doi:10.1021/jp400648q' 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. The Journal of Physical Chemistry C. American Chemical Society (ACS). https://doi.org/10.1021/jp400648q' 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.” The Journal of Physical Chemistry C. American Chemical Society (ACS), 2013. https://doi.org/10.1021/jp400648q.' ieee: 'T.-C. Lin 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,” The Journal of Physical Chemistry C, vol. 117, no. 18. American Chemical Society (ACS), pp. 9416–9430, 2013.' 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.” The Journal of Physical Chemistry C, vol. 117, no. 18, American Chemical Society (ACS), 2013, pp. 9416–30, doi:10.1021/jp400648q.' 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. date_created: 2019-05-03T09:40:31Z date_published: 2013-05-09T00:00:00Z date_updated: 2021-01-12T08:07:17Z day: '09' doi: 10.1021/jp400648q extern: '1' intvolume: ' 117' issue: '18' language: - iso: eng month: '05' oa_version: None page: 9416-9430 publication: The Journal of Physical Chemistry C publication_identifier: issn: - 1932-7447 - 1932-7455 publication_status: published publisher: American Chemical Society (ACS) quality_controlled: '1' status: public title: 'Molecular origins of the high-performance nonlinear optical susceptibility in a phenolic polyene chromophore: Electron density distributions, hydrogen bonding, and ab initio calculations' type: journal_article user_id: 3E5EF7F0-F248-11E8-B48F-1D18A9856A87 volume: 117 year: '2013' ...