Phenyltetraene-Based Nonlinear Optical Chromophores with Enhanced Chemical Stability and Electrooptic Activity

Abstract

"Push-pull" phenyltetraene-based chromophores are too sensitive to be incorporated into Diels-Alder-type cross-linkable polymers due to the reactivity of its diene segment with maleimides. A facile synthetic route has been explored to incorporate a methoxy group into the R position of such chromophores, which reduces their diene reactivity during the poling and lattice hardening process. The poled polymers with one of such chromophores doped in a cross-linked polymer lattice showed ultrahigh electro-optic activities, up to 306 pm/V at 1310 nm.

Supramolecular Self‐Assembled Dendritic Nonlinear Optical Chromophores: Fine‐Tuning of Arene–Perfluoroarene Interactions for Ultralarge Electro‐Optic Activity and Enhanced Thermal Stability

“…[17] Here, we develop a new series of supramolecular self-assembled dendritic EO chromophores (TED1, TED2, and TED3, where TEDs are tetraene-chromophone-containing dendrimers) derived from a combination of a highly efficient, chemically stable chromophore moiety [17] and various complementary aryl/perfluoroaryl dendrons on the periphery allowing the desired ArH-ArF interaction. The incorporated perfluoroaryl dendron, built from a pentafluorophenyl ring, was situated on the p-bridge of the chromophore, but not on the donor-end, considering its electron-deficient characteristics.…”

“…Such a route has been well established for the synthesis of phenyltetraene-based NLO chromophores. [17] The pentafluorophenyl-and various aryl dendrons were then sequentially introduced to the p-bridge and donor-end of the trienal by carbodiimide-mediated esterification following the procedure described in the literature. [15] Finally, efficient condensation of the dendronized trienal with a strong CF 3 -TCF-type acceptor [19] afforded the desired chromophores TED1-3 in 31-46% overall yields.…”

“…UV-vis spectra were recorded using a Perkin-Elmer spectrophotometer (Lambda 9 UV/Vis/NIR). Chromophore 10 and AJL33 were prepared according to the methods described for TED1-3 and in the literature [17], respectively.…”

Copper-catalyzed Huisgen cycloaddition reactions used to incorporate NLO chromophores into high Tg Side-Chain Polymers for Electro-Optics

“…Lots of organic NLO materials have been prepared in the recent years and some of them show us large EO coefficients above 200 pm/V, but there are still some problems hindering their practical application in the future: the contradiction between large electro-optic coefficient and oriental stability was the most important one. Now, most of the large EO coefficients reported are measured in guest host systems, Strong intermolecular dipole induced interaction and weak binding effect of polymer chains make the NLO materials with weak oriental stability [8][9][10][11]. Through attaching NLO chromophores to polymers as side chain is considered as an effective way to increase the materials' oriental stability, efficiency of the attaching reaction, effect of byproduct on communication light and materials' optical stability all hindered the development of side chain EO polymers.…”

Polymer-Based Hybrid-Integrated Photonic Devices for Silicon On-Chip Modulation and Board-Level Optical Interconnects

“…For example, CDL1/PMMA, an EO polymer with γ 33 =60pm/V, was used to achieve V π =0.8V [10]. Another EO polymer with a very large γ 33 =306pm/V was developed through controlled molecular self-assembly and lattice hardening [13]. In comparison, the γ 33 of LiNbO 3 is only about 30pm/V at 1300nm.…”