{"year":"2013","doi":"10.1021/jp400648q","page":"9416-9430","user_id":"3E5EF7F0-F248-11E8-B48F-1D18A9856A87","publication_status":"published","author":[{"last_name":"Lin","first_name":"Tze-Chia","full_name":"Lin, Tze-Chia"},{"full_name":"Cole, Jacqueline M.","first_name":"Jacqueline M.","last_name":"Cole"},{"first_name":"Andrew P","id":"4AD6785A-F248-11E8-B48F-1D18A9856A87","last_name":"Higginbotham","full_name":"Higginbotham, Andrew P","orcid":"0000-0003-2607-2363"},{"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"},{"full_name":"Seo, Ji-Youn","first_name":"Ji-Youn","last_name":"Seo"},{"full_name":"Lee, Seung-Chul","last_name":"Lee","first_name":"Seung-Chul"},{"full_name":"Clays, Koen","last_name":"Clays","first_name":"Koen"},{"first_name":"O-Pil","last_name":"Kwon","full_name":"Kwon, O-Pil"}],"date_published":"2013-05-09T00:00:00Z","date_created":"2019-05-03T09:40:31Z","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"}],"extern":"1","status":"public","type":"journal_article","date_updated":"2021-01-12T08:07:17Z","_id":"6370","citation":{"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.","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>.","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.","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>.","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>","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.","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>"},"publication_identifier":{"issn":["1932-7447","1932-7455"]},"quality_controlled":"1","title":"Molecular origins of the high-performance nonlinear optical susceptibility in a phenolic polyene chromophore: Electron density distributions, hydrogen bonding, and ab initio calculations","language":[{"iso":"eng"}],"oa_version":"None","publication":"The Journal of Physical Chemistry C","issue":"18","month":"05","day":"09","publisher":"American Chemical Society (ACS)","intvolume":"       117","volume":117}