Donor-substituted triaryl-1,3,5-triazinanes-2,4,6-triones: octupolar NLO-phores with a remarkable transparency–nonlinearity trade-off

Abstract

We report in this letter the measurement of the hyperpolarizabilities of a series of donor-substituted triaryl-1,3,5-triazinanes-2,4,6-triones by hyper Rayleigh scattering (HRS). A remarkable transparency-nonlinearity trade-off is evidenced for these octupolar NLO-phores which might be accessed in a straightforward synthetic way and in a few steps from commercial isocyanates. Scheme 1 Scheme 2

Triaryl‐1,3,5‐triazinane‐2,4,6‐triones (Isocyanurates) Peripherally Functionalized by Donor Groups: Synthesis and Study of Their Linear and Nonlinear Optical Properties

“…This lack of interest is surprising because, owing to their planar D 3 h or twisted pseudo‐ D 3 symmetry ( A ; Scheme ), these compounds might exhibit significant second‐10 and third‐order11 nonlinear optical (NLO) activities when the central electron‐attracting isocyanurate core is symmetrically decorated with electron‐releasing arms, likewise to related structures based on 1,3,5‐ and 2,4,6‐substituted phenyl derivatives ( B ; Scheme ) 12. In accordance with the first expectation, we have recently shown by hyper Raleigh scattering (HRS) that derivatives such as 1‐X and 2‐X (X=OMe, NMe 2 ) possess remarkable hyperpolarizabilities 14. Given that such octupolar structures might also present good activities for specific third‐order NLO properties, such as two‐photon absorption (TPA),11 we have now completed our previous report on these compounds14 by studying their luminescence and have subsequently used their luminescence to determine the TPA cross sections of selected derivatives.…”

“…In accordance with the first expectation, we have recently shown by hyper Raleigh scattering (HRS) that derivatives such as 1‐X and 2‐X (X=OMe, NMe 2 ) possess remarkable hyperpolarizabilities 14. Given that such octupolar structures might also present good activities for specific third‐order NLO properties, such as two‐photon absorption (TPA),11 we have now completed our previous report on these compounds14 by studying their luminescence and have subsequently used their luminescence to determine the TPA cross sections of selected derivatives. Although the synthesis of some of these cyclotrimers has been briefly reported, a more complete account of their synthesis is now disclosed.…”

“…Synthesis and characterization : Although para ‐functional arylisocyanurates 1‐X that feature electron‐releasing X substituents (X=OMe, NH 2 , NMe 2 ) at the periphery were initially targeted for their second‐order NLO properties,14 some derivatives that feature strongly electron‐attracting substituents, para ‐functional arylisocyanurates 1‐X (X=NO 2 , CN), were also targeted to complete our experimental data on these compounds. The synthesis of most of these arylisocyanurates (X=NO 2 , CN Br, OMe, NMe 2 ) was achieved by directly cyclotrimerizing the corresponding isocyanates, when commercially available [Scheme , Eq.…”

“…Nonlinear optical properties : The hyperpolarizabilities of the cyclotrimers 1‐X and 2‐X featuring electron‐releasing groups at their periphery have been previously determined by the hyper Raleigh scattering (HRS) method in solution (Table 5), except for 1‐NH 2 and 2‐NH 2 which turned out to be not soluble enough 14. The corresponding static hyperpolarizabilities, denoted as β HRS (0) hereafter, were determined by using the simple three‐level model [Eqs.…”

Hexaazatriphenylene (HAT) derivatives: from synthesis to molecular design, self-organization and device applications

“…207 However, Zyss and coworkers 208 showed that octupolar molecules with C 3 symmetry exhibit first hyperpolarizability comparable to those of the donor-acceptor dipoles and a great deal of interest have been devoted to the use of these types of systems for NLO applications. 210 In this respect, the HAT moiety has been identified as a good scaffold to build octupolar systems and the NLO properties of some HAT derivatives (101-103, Fig. 210 In this respect, the HAT moiety has been identified as a good scaffold to build octupolar systems and the NLO properties of some HAT derivatives (101-103, Fig.…”