---
_id: '92'
abstract:
- lang: eng
text: 'Advanced organic nonlinear 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-π-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
nonlinear 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-CH3, Y = 4-CH3; 3, X = 4-NO2, Y = 2,5-OCH3; 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 three methods delivered consistent values of β, and based on these results,
3 should hold the most promise for NLO applications. The correlation between the
molecular structure of these geminal amido esters and their linear and nonlinear
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.'
acknowledgement: J.M.C. thanks the 1851 Royal Commission of the Great Exhibition for
a Design Fellowship, hosted by Argonne National Laboratory where work done was supported
by the DOE Office of Science, Office of Basic Energy Sciences, under Contract No.
DE-AC02-06CH11357. T.-C.L acknowledges the Taiwanese Government for a Studying Abroad
Scholarship. C.M.A is indebted to the EPSRC UK for a DTA Ph.D. studentship (Grants
EP/J500380/1 and EP/L504920/1). Y.T. is grateful for a Cavendish-NUDT Scholarship.
The Swiss-Norwegian Collaborative Research Group at the ESRF, Grenoble, France,
is thanked for access to synchrotron facilities. The OPAL reactor, ANSTO, Australia,
is acknowledged for access to neutron scattering facilities via a program proposal,
ID 1236. J.P-M. is grateful to Skidmore College for supporting this work via a full-year
sabbatical with enhancement. All authors thank the EPSRC UK National Service for
Computational Chemistry Software (NSCCS) and acknowledge contributions from its
staff in supporting this work.
author:
- first_name: Jaqueline
full_name: Cole, Jaqueline
last_name: Cole
- first_name: Tzechia
full_name: Lin, Tzechia
last_name: Lin
- first_name: Christopher
full_name: Ashcroft, Christopher
last_name: Ashcroft
- first_name: Javier
full_name: Pérez Moreno, Javier
last_name: Pérez Moreno
- first_name: Yizhou
full_name: Tan, Yizhou
last_name: Tan
- first_name: Perumal
full_name: Venkatesan, Perumal
last_name: Venkatesan
- 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: Philip
full_name: Pattison, Philip
last_name: Pattison
- first_name: Alison
full_name: Edwards, Alison
last_name: Edwards
- first_name: Ross
full_name: Piltz, Ross
last_name: Piltz
- first_name: Koen
full_name: Clays, Koen
last_name: Clays
- first_name: Andivelu
full_name: Ilangovan, Andivelu
last_name: Ilangovan
citation:
ama: Cole J, Lin T, Ashcroft C, et al. Relating the structure of geminal Amido Esters
to their molecular hyperpolarizability. Journal of Physical Chemistry C.
2016;120(51):29439-29448. doi:10.1021/acs.jpcc.6b10724
apa: Cole, J., Lin, T., Ashcroft, C., Pérez Moreno, J., Tan, Y., Venkatesan, P.,
… Ilangovan, A. (2016). Relating the structure of geminal Amido Esters to their
molecular hyperpolarizability. Journal of Physical Chemistry C. American
Chemical Society. https://doi.org/10.1021/acs.jpcc.6b10724
chicago: Cole, Jaqueline, Tzechia Lin, Christopher Ashcroft, Javier Pérez Moreno,
Yizhou Tan, Perumal Venkatesan, Andrew P Higginbotham, et al. “Relating the Structure
of Geminal Amido Esters to Their Molecular Hyperpolarizability.” Journal of
Physical Chemistry C. American Chemical Society, 2016. https://doi.org/10.1021/acs.jpcc.6b10724.
ieee: J. Cole et al., “Relating the structure of geminal Amido Esters to
their molecular hyperpolarizability,” Journal of Physical Chemistry C,
vol. 120, no. 51. American Chemical Society, pp. 29439–29448, 2016.
ista: Cole J, Lin T, Ashcroft C, Pérez Moreno J, Tan Y, Venkatesan P, Higginbotham
AP, Pattison P, Edwards A, Piltz R, Clays K, Ilangovan A. 2016. Relating the structure
of geminal Amido Esters to their molecular hyperpolarizability. Journal of Physical
Chemistry C. 120(51), 29439–29448.
mla: Cole, Jaqueline, et al. “Relating the Structure of Geminal Amido Esters to
Their Molecular Hyperpolarizability.” Journal of Physical Chemistry C,
vol. 120, no. 51, American Chemical Society, 2016, pp. 29439–48, doi:10.1021/acs.jpcc.6b10724.
short: J. Cole, T. Lin, C. Ashcroft, J. Pérez Moreno, Y. Tan, P. Venkatesan, A.P.
Higginbotham, P. Pattison, A. Edwards, R. Piltz, K. Clays, A. Ilangovan, Journal
of Physical Chemistry C 120 (2016) 29439–29448.
date_created: 2018-12-11T11:44:35Z
date_published: 2016-12-05T00:00:00Z
date_updated: 2021-01-12T08:21:55Z
day: '05'
doi: 10.1021/acs.jpcc.6b10724
extern: '1'
intvolume: ' 120'
issue: '51'
language:
- iso: eng
month: '12'
oa_version: None
page: 29439 - 29448
publication: Journal of Physical Chemistry C
publication_status: published
publisher: American Chemical Society
publist_id: '7962'
quality_controlled: '1'
status: public
title: Relating the structure of geminal Amido Esters to their molecular hyperpolarizability
type: journal_article
user_id: 3E5EF7F0-F248-11E8-B48F-1D18A9856A87
volume: 120
year: '2016'
...