Anissa Amar

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.

The linear optical (LO) and nonlinear optical (NLO) properties of a series of isocyanurates functionalized by donor arms at the periphery are reported herein. These octupolar derivatives were obtained in a straightforward way from commercial isocyanate derivatives and were fully characterized. Although several of these compounds are known, those that exhibited the largest NLO activities are all new compounds. In terms of second-order activity, several of these derivatives exhibit remarkable activity/transparency tradeoffs. In terms of third-order activity, the longer derivatives with the stronger donor groups (X = NH(2), NMe(2), or NPh(2)) were shown to possess significant two-photon absorption cross sections. These strongly luminescent derivatives exhibit two-photon absorption cross sections up to 410 GM. DFT computations were also conducted to unravel their electronic structures and to rationalize their NLO properties. To our knowledge, the present study is the first concerned with the nonlinear optical properties of these original cyclotrimers.

Aggregation Effect on the Luminescence Properties of Phenylbipyridine Pt(II) Acetylide Complexes. A Theoretical Prediction with Experimental Evidence

We report a combined theoretical and experimental study of both the structural and optical properties of phosphorescent cyclometalated square-planar (phenylbipyridyl)platinum(II) acetylide complexes, namely (Pt(tBu2-ĈN̂N)(C≡C-Ph)] and (Pt(hex2-ĈN̂N)(C≡C-thienyl)] that exhibit, at high concentrations, an additional emission band at longer wavelength. The geometry optimizations of both the ground and the lowest triplet excited states of the considered monomers and different possible dimers have been performed in solution using several density functional theory (DFT) functionals corrected for dispersion effects. For the dimers, which are shown to exhibit a head-to-tail configuration, a significant shortening of the Pt···Pt distance, compared to that in the ground state, is observed in the first triplet state. Moreover, we show that trimeric species are highly improbable in solution. The UV-visible absorption spectra of the complexes are well rationalized using a vertical time-dependent DFT (TD-DFT) protocol relying on a global hybrid exchange-correlation functional. Finally, the new emission band at high concentration of the complexes can be assigned to a metal-metal to ligand charge transfer excited state ((3)MMLCT).

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

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.

Photoisomerisation in Aminoazobenzene-Substituted Ruthenium(II) Tris(bipyridine) Complexes: Influence of the Conjugation Pathway

Transition-metal complexes containing stimuli-responsive systems are attractive for applications in optical devices, photonic memory, photosensing, as well as luminescence imaging. Amongst them, photochromic metal complexes offer the possibility of combining the specific properties of the metal centre and the optical response of the photochromic group. The synthesis, the electrochemical properties and the photophysical characterisation of a series of donor-acceptor azobenzene derivatives that possess bipyridine groups connected to a 4-dialkylaminoazobenzene moiety through various linkers are presented. DFT and TD-DFT calculations were performed to complement the experimental findings and contribute to their interpretation. The position and nature of the linker (ethynyl, triazolyl, none) were engineered and shown to induce different electronic coupling between donor and acceptor in ligands and complexes. This in turn led to strong modulations in terms of photoisomerisation of the ligands and complexes.

Diphenylamino-substituted tristyryl vs. triphenyl isocyanurates: improved conjugation has minimal impact on two-photon absorption

This contribution reports the synthesis of C87H60N6O3 (3-NPh2), the tristyryl analogue of the triphenylisocyanurate C81H54N6O3 (2-NPh2) which was previously demonstrated to be an active two-photon absorber. Contrary to expectation, planarization and extension of the central π-system does not lead to a marked improvement of the two-photon absorption cross-section.

New 2-pyrone-based hydrazones: Synthesis, spectral characterisation, UV–visible study and evaluation of the antiradicalar activity

ABSTRACT The synthesis of new 2-pyrone-based hydrazones has been prepared by the coupling of 6-methyl-2H-furo[3,2-c]pyran-3,4-dione with diazonium salts, obtained by diazotization of aniline derivatives. The structure of all compounds was established by spectroscopic methods, and the structure of the more stable conformer was theoretically confirmed by the potential energy profile analysis. The prepared 2-pyrone-based hydrazone dyes were acetylated and both groups of compounds showed moderate to good radical scavenging activity. GRAPHICAL ABSTRACT