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Title: Relating the structure of geminal amido esters to their molecular hyperpolarizability

Advanced organic non-linear optical (NLO) materials have attracted increasing attention due to their multitude of applications in modern telecommunication devices. Arguably the most important advantage of organic NLO materials, relative to traditionally used inorganic NLO materials, is their short optical response time. Geminal amido esters with their donor-x-acceptor (D-π-A) architecture exhibit high levels of electron delocalization and substantial intramolecular charge transfer, which should endow these materials with short optical response times and large molecular (hyper)polarizabilities. In order to test this hypothesis, the linear and second-order non-linear optical properties of five geminal amido esters, ( E)-ethyl 3-(X-phenylamino)-2-(Y-phenylcarbamoyl)acrylate (1: X = 4-H,Y = 4-H; 2: X= 4-CH 3, Y = 4-CH 3; 3: X = 4-NO 2, Y = 2,5-OCH 3; 4: X = 2-Cl, Y = 2-Cl; 5: X = 4-Cl, Y = 4-Cl) were synthesized and characterized, whereby NLO structure-function relationships were established including intramolecular charge transfer characteristics, crystal field effects, and molecular first hyperpolarizabilities β. Given the typically large errors (10-30%) associated with the determination of (β) coefficients, three independent methods were used: i) density functional theory, ii) hyper-Rayleigh scattering, and iii) high-resolution X-ray diffraction data analysis based on multipolar modeling of electron densities at each atom. These threemore » methods delivered consistent values of β, and based on these results, 3 should hold the most promise for NLO applications. In conclusion, the correlation between the molecular structure of these geminal amido esters and their linear and non-linear optical properties thus provide molecular design guidelines for organic NLO materials; this leads to the ultimate goal of generating bespoke organic molecules to suit a given NLO device application.« less
ORCiD logo [1] ;  [2] ;  [2] ;  [3] ;  [2] ;  [4] ;  [2] ;  [5] ;  [6] ;  [6] ;  [7] ;  [4]
  1. Univ. of Cambridge, Cambridge (United Kingdom); Rutherford Appleton Lab., Oxfordshire (United Kingdom); Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Univ. of Cambridge, Cambridge (United Kingdom)
  3. Univ. of Leuven, Leuven (Belgium); Skidmore College, Saratoga Springs, NY (United States)
  4. Bharathidasan Univ., Tamilnadu (India)
  5. European Synchrotron Radiation Facility (ESRF), Grenoble (France)
  6. Australian Centre for Neutron Scattering, Lucas Heights (Australia)
  7. Univ. of Leuven, Leuven (Belgium)
Publication Date:
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 51; Journal ID: ISSN 1932-7447
American Chemical Society
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
OSTI Identifier: