Designing Efficient Azobenzene and Azothiophene Nonlinear Optical Photochromes - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Physical Chemistry C Année : 2014

Designing Efficient Azobenzene and Azothiophene Nonlinear Optical Photochromes

Résumé

The present contribution constitutes an extensive density functional theory (DFT) investigation of the nonlinear optical (NLO) properties of a large number of molecules belonging to the azobenzene and azothiophene families of photochromic compounds which can act as NLO switches. Toward the design of systems simultaneously presenting both large total nonlinear response values, beta(tot), and large contrast, beta(ratio), between the cis and trans isomers, we have focused not only on the monomers but also on azobenzene dimers, the latter containing two N=N bonds along the molecular backbone. After it was established that the inclusion of implicit solvation is not important in drawing qualitative conclusions on the NLO switching ability for the investigated systems, gas-phase calculations have shown that for the asymmetric pushpull azobenzene and azothiophene candidates, the combination of strong donating groups such as NPh2, N(Ph-OMe)(2), and N(Ph-NMe2)(2) with the dicyanoethene group CH=C(C=N)(2) as an acceptor delivers large ?trans (150-217 x 10(-30) esu) and non-negligible beta(cis) (18-55 x 10(-30) esu) values as well as substantial contrast, beta(ratio) (3.9-8.7). For the investigated double azobenzenes, it is found that, with a careful choice of donor and acceptor groups, the contrast, beta(ratio), can be significantly increased compared to that of the monomers while maintaining large beta values that facilitate their detection with standard experimental techniques (e.g., electric-field-induced second-harmonic generation). Our results set the stage on which further theoretical and experimental studies can be based in the search for efficient and versatile NLO switches.
Fichier non déposé

Dates et versions

hal-01389018 , version 1 (27-10-2016)

Identifiants

Citer

Titouan Jaunet-Lahary, Agisilaos Chantzis, Kathy J. Chen, Adele D. Laurent, Denis Jacquemin. Designing Efficient Azobenzene and Azothiophene Nonlinear Optical Photochromes. Journal of Physical Chemistry C, 2014, 118 (49), pp.28831-28841. ⟨10.1021/jp510581m⟩. ⟨hal-01389018⟩
34 Consultations
0 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More