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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Interpreting the First-Order Electronic Hyperpolarizability for a Series of Octupolar Push-Pull Triarylamine Molecules Containing Trifluoromethyl

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Author(s):
Vivas, Marcelo G. [1, 2] ; Silva, Daniel L. [3] ; Rodriguez, Ruben D. F. [1] ; Canuto, Sylvio [4] ; Malinge, Jeremy [5] ; Ishow, Elena [6] ; Mendonca, Cleber R. [1] ; De Boni, Leonardo [1]
Total Authors: 8
Affiliation:
[1] Univ Sao Paulo, Inst Fis Sao Carlos, BR-13560970 Sao Carlos, SP - Brazil
[2] Univ Fed Alfenas, Inst Ciencia Tecnol, BR-37715400 Pocos De Caldas, MG - Brazil
[3] Univ Fed Sao Carlos, Dept Ciencias Nat Matemat & Educ, BR-13600970 Araras, SP - Brazil
[4] Univ Sao Paulo, Inst Fis, BR-05314970 Sao Paulo, SP - Brazil
[5] Ecole Normale Super, PPSM UMR CNRS 8531, F-94235 Cachan - France
[6] Univ Nantes, CEISAM UMR CNRS 6230, F-44322 Nantes - France
Total Affiliations: 6
Document type: Journal article
Source: Journal of Physical Chemistry C; v. 119, n. 22, p. 12589-12597, JUN 4 2015.
Web of Science Citations: 8
Abstract

In this present paper, we investigate the relationship between the dynamic first-order hyperpolarizability (DFH, or beta(HRS)) of a triarylamine core bearing two 3,3'-bis(trifluoromethyl)phenyl arms and the nature of a third group containing distinct electron withdrawing strength (H < CN < CHO < NO2 < Cyet < Vin). For that, we have combined hyper-Rayleigh scattering (HRS) experiments with picosecond pulse train at 1064 nm and quantum chemical calculations at the density functional theory (DFT) level. The beta(HRS) values exhibited pronounced enhancement from 56 x 10(-30) cm(5)/esu (EWG = CN) up to similar to 400 X 10(-30) cm(5)/esu (EWG = Vin) due to the increase in the degree of donor-acceptor charge transfer concomitant with the intensification of the resonance enhancement effect observed when the scattered photon (2w = 532 nm) approaches, in energy, the lowest energy band of chromophores. Furthermore, our experimental results suggest that the CF3 group has a significant effect on the beta(HRS), since we observed a considerable increase in this parameter (at least 30% higher) for CF(3)EWG molecules as compared to their homologous tBu.EWG derivatives, recently investigated. Finally, the beta(HRS) results were compared with theoretical results provided by the coupled perturbed Hartree-Fock method implemented at the DFT level of theory and combined with a polarizable continuum model to take into account the solvent environment. The theoretical results allowed us to evaluate the effects of solvent-induced polarization and frequency dispersion on the first-order hyperpolarizability of the molecules and their molecular anisotropy (or dipolar/octupolar contributions). (AU)

FAPESP's process: 09/11810-8 - Study of solvent effect on the one- and two-photon absorption spectra of conjugated organic molecules.
Grantee:Daniel Luiz da Silva
Support Opportunities: Scholarships in Brazil - Post-Doctoral
FAPESP's process: 11/12399-0 - Femtosecond pulses applied to nonlinear optics: spectroscopy, pulse shaping and microfabrication
Grantee:Cleber Renato Mendonça
Support Opportunities: Research Projects - Thematic Grants