New trans-stilbene derivatives with large two-photon absorption cross-section and non-linear optical susceptibility values – a theoretical investigation

Abstract

A detailed theoretical study of linear and non-linear optical susceptibilities (NLOS), one- and two-photon absorption (OPA and TPA) properties for a series of push-pull trans-stilbene (TSB) derivatives with introduction of different electron donor (D) and acceptor (A) groups on either side of the TSB ring system is presented. The objective of the work is to design new TSB derivatives with large TPA cross-section values and to explore their linear and non-linear optical susceptibilities, OPA and TPA properties. We have used linear and quadratic response theory methods and CAM-B3LYP functional in conjunction with the 6-31+G* basis set for all property calculations. We have explained the results of the first hyperpolarizability and TP transition probability using two-state model (2SM) calculations, the results of which are in excellent agreement with the response theory methods. The TP tensor elements have been analysed to explain the large TP activity of molecules. Orbitals involved in the transition processes have been studied both qualitatively (molecular orbital pictures) and quantitatively (Λ-values) in order to explain the nature of charge transfer in different TSB derivatives. The study reveals that the novel derivatives TSBD-10, TSBD-11, TSBD-12 and TSBD-13 have large non-linear optical susceptibilities and TPA cross-section values, the largest being found for TSBD-13 (5560 G.M.).

Carborane–stilbene dyads: the influence of substituents and cluster isomers on photoluminescence properties

“…14,16 The main objective of adding a terminal styrene moiety to the carborane cluster was to have a suitable group for further functionalization to develop conceptually different light-dependent macromolecules, like dendrimers or octasilsesquioxanes, 17,18 as well as small fluorescent molecules. 16 Due to the interest generated by the application of stilbene derivatives [19][20][21] in fields such as biomedicine, [22][23][24][25] electro-optic materials, 26 LEDs, 27 non-linear optics 28 among others; we aimed to develop new carborane-stilbene compounds from our previous styrene derivatives to study the influence of the C c -substituted cluster on their photophysical properties. In a previous work, we synthesized stilbene-carborane triads in which o-or m-carborane clusters are linked to two stilbene units through a methylene spacer.…”

Solvent effects on static polarizability, static first hyperpolarizability and one- and two-photon absorption properties of functionalized triply twisted Möbius annulenes: a DFT study

“…semiconductor quantum dots), 44 organometallics, 45 and (in)organic molecules. [46][47][48][49][50][51][52] However, extended p-conjugation, easy tailoring, ultra-fast response, lower dielectric constant and better processable characters make the organic molecules most favourable for NLO material design. In these molecules, strong donor and acceptor groups at suitable positions ensure efficient polarization, which is used as a general strategy for material design.…”

Intramolecular charge transfer enhanced optical limiting in novel hydrazone derivatives with a D1–D–Ai–π–A structure

“…This method is called pseudo-wavefunction formulation of LR-TDDFT(PWF-TDDFT), 44,45 which also has been widely applied in the simulation of RIXS spectra. 45,46 For linearly polarized light with parallel polarization, the 2PA strength d 2PA is defined as 47,48 d 2PA ¼ 1 15…”

“…For linearly polarized light with parallel polarization, the 2PA strength δ 2PA is defined as 47,48 and the 3PA strength δ 3PA is defined as 49 where S is the 2PA and 3PA transition moment.…”