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Two novel nonlinear optical (NLO) chromophores JC-T-TCF and JC-F-TCF utilizing tetramethyljulolidine-based coumarin and tricyanofuran(TCF) as the electron donor and acceptor, respectively, were designed and synthesized. The two chromophores were linked with different π conjugated electron bridge (thiophene group and furan group), which provide the opportunity to study the structure–property relationship of coumarin-based chromophores. Both the novel obtained chromophores exhibited reasonable stability and solvatochromic effect. The theoretical calculation results indicated that both chromophores possess microscopic hyperpolarizability (β) in excess of 320 × 10−30esu, and the chromophore JC-T-TCF utilizing thiophene group as the electron bridge exhibited obviously larger β value (456.8 × 10−30esu). The larger β value, combination with the larger µ value, endowed JC-T-TCF with larger electro-optic activity of 70 pm V−1 at the wavelength of 1310 nm in the guest–host films of chromophores doped into PMMA, which provide the potential application opportunity in the field of optical waveguide devices. [ABSTRACT FROM AUTHOR]

Developing new organic chromophores with a large electro-optic coefficient (r33) is highly desirable for fabricating electro-optic (EO) materials. Building on the fact that the 1,1,7,7-tetramethyl julolidine fused furan ring is a good electron donor and lengthening the π-bridge of a chromophore with a five-membered heterocycle ring could lead to the improvement of r33. Here we design and synthesize two new chromophores C1 and C2 by using a 1,1,7,7-tetramethyl julolidine fused furan ring as the electron donor and 2-(3-cyano-4,5,5-trimethyl-5H-furan-2-ylidene)-malonitrile (TCF) as the acceptor, but with two different π-bridges (furan-vinylene and thiophene-vinylene accordingly). When doping C1 or C2 into PMMA with a loading density of 20 wt%, the poled films containing C1 or C2 exhibited an r33 value of 75 pm V−1 and 94 pm V−1, respectively. When compared with chromophore C3 (an ene unit as the π-bridge, r33 = 52 pm V−1), an enhanced r33 of C1 and C2 was achieved due to the introduction of a heterocycle ring into the π-bridge. This work uncovers the influence of the heterocycle ring on the julolidine fused furan based chromophore's physical and chemical properties and demonstrates that the new chromophores are a promising candidate for EO material application. [ABSTRACT FROM AUTHOR]

Abstract Monolithic electro-optic (EO) molecular glasses are promising materials for optical waveguide device owing to their high chromophore loading density, high refractive indices and large EO coefficients (r 33 values) for the optimization of in-device figure of merit (n 3 r 33). However, the stability of EO molecular glasses including the poling induced r 33 stability, chemical stability under both high temperature and high voltage in poling is still an obstruction for their real application. Herein, we used the chemical structural optimization, by means of introducing a large conjugated electron-bridge indacenodithiophene (IDT), to synthesize a monolithic EO molecular glass IDTC. Comprehensive properties of excellent glass-forming ability, high thermal stability (T d = 315 °C), and high glass transition temperature (T g = 137 °C) was achieved in monolithic IDTC thin films. More significantly, refractive index of monolithic film was exceptionally high (n = 1.8294 @ 1310 nm and n = 1.7645 @1550 nm). The poled IDTC film exhibited the r 33 value of 87.6 pm/V with large figure of merit (n 3 r 33 : 536 pm/V @1310 nm), and the EO activity can be retained over 85% of the initial value after 300 h annealing at 85 °C. Meanwhile, it was found that there is no decomposition of IDTC in poled films after high temperature and high voltage poling as well as long term annealing. The poled chromophores are recyclable EO materials for the sustainable application in low-cost EO devices. Highlights • Novel EO molecular glass IDTC based on indacenodithiophene was synthesized. • IDTC showed excellent thermal stability and temporal stability of EO activity. • IDTC exhibited high figure of merits value of 536 pm/V (n3r 33) at 1310 nm. [ABSTRACT FROM AUTHOR]

Abstract Novel nonlinear optical chromophores JC-TCF and JC-FTCF using tetramethyljulolidine-based coumarin as the electron-donor and tricyanofuran derivatives as the electron acceptors were designed, synthesized and investigated. The obtained chromophores own good solubility in common solvents, and good compatibility with host polymers. The chromophores also have good thermal stability, and the decomposition temperature exceed 200 °C. The UV–vis spectra indicated that JC-TCF and JC-FTCF possess good intramolecular charge transfer ability. Density functional theory (DFT) was used to study the energy gap and first-order hyperpolarizability(β). After contact poling, the guest-host polymer films of polymethyl methacrylate containing 20% wt JC-TCF and 20% wt JC-FTCF exhibited the highest electro-optic coefficient (r 33) up to 40 p.m./V and 76 p.m./V respectively, and the results indicated the chromophores' microscopic β value could be effectively translated to macroscopic EO activity, and the tetramethyljulolidine-based coumarin could be an useful candidate in the development of NLO materials. Highlights • Julolidine-based coumarin was used as electron-donor in design of NLO materials. • The coumarin's good electron-donation ability obviously enhanced the NLO properties. • The obtained materials exhibited better EO activity compared to the FTC chromophores. • The maximum EO activity of reported NLO chromophores reached to 76 p.m./V. • Coumarin could be an useful candidate in the development of NLO materials. [ABSTRACT FROM AUTHOR]

Abstract: A novel nunchaku-like organic second order nonlinear optical chromophore containing a D–π–A backbone and a rigid biphenylene unit was prepared. The UV–vis absorption spectra studies demonstrated that the large rigid structure could suppress dipole–dipole interactions effectively. The electro-optic coefficient of a poled film containing 20% wt of the new dye doped in amorphous polycarbonate afforded a value of 39 pm/V at 1310 nm. Compared with results obtained from a similar D–π–A chromophore without the rigid isolated group, the new dye gave better performance. Moreover, the electro-optic film prepared with the new dye gave greater temporal stability, compared to a similar D–π–A doped poled film that was reported previously. These results indicated that the introduction of a biphenylene group could effectively reduce the intermolecular electrostatic interactions and aid the alignment of the chromophores. [Copyright &y& Elsevier]

A new series of Y-type polyurethanes containing different concentrations of nonlinear optical (NLO) chromophore with aniline donor and tricyanofurane (TCF) acceptor have been successfully prepared, and characterized by FTIR, UV-Vis, and 1H-NMR spectra. New polyurethanes were synthesized with different chromophore contents by introducing diol N, N-dihydroxyethylaniline or 4-[ N, N-(dihydroxyethyl)amino]benzaldehyde. These NLO polyurethanes exhibit good film forming property and high thermal stability up to 281°C. The highest electro-optic coefficient ( r33) of polymers is up to 39 pm V−1 measured by simple reflection technique at 1310 nm, and the temporal stability of the poling-induced order at elevated temperature of 80°C was much improved through the introducing of hydrogen bonding interaction in this system. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013 [ABSTRACT FROM AUTHOR]

Three chromophores with tricyanofuran and tricyanopyrroline electron acceptors were synthesized and doped in high glass transition temperature ( T) polymer poly( N-(4-acetoxylphenyl)maleimide-co-styrene, NAPMI-co-ST). The electro-optic (EO), optical, and thermal properties of the doped poly(NAPMI-co-ST) were characterized and discussed. After being corona poled under 12 kV, this high T polymer material showed excellent EO activity and thermal stability. The highest EO coefficient ( r) reached 48.2 pm V (1,310 nm) and could remain 90 % of the original value for 100 h at 85 °C. The EO coefficient was relatively higher compared with other high T EO polymers. The thermal stability was also very good and the manufacture process was convenient and applicable for device fabrication. [ABSTRACT FROM AUTHOR]

Abstract A series of highly polarizable nonlinear optical (NLO) chromophores ZJ1-4 with three different configurations, including rod-like, Y-shaped and X-shaped configurations, have been synthesized with facile routes and systematically studied. The resulted chromophores exhibited excellent thermal stabilities. The relationship between molecular configuration and NLO activity was analyzed from the theoretical calculation and experiment. The molecular dipole moment of chromophore ZJ4 was enhanced by X-shaped structure with two acceptors. Meanwhile, the tendency of forming anti-parallel interactions could be inhibited by disk-like molecular configuration with larger steric hindrance. ZJ4 exhibits the largest EO activity of 103 pm/V, and both of molecular and material NLO properties are improved for the chromophore ZJ4 with the X-shaped configuration compared with corresponding benchmark chromophore ZJ1 with rod-like molecular structure. Highlights • Four highly polarizable nonlinear optical chromophores ZJ1-ZJ4 had been synthesized. • The chromophores ZJ1-ZJ4 have rod-like, Y-shaped and X-shaped configurations. • The r 33 value of the X-shaped chromophore ZJ4 is much higher than others. [ABSTRACT FROM AUTHOR]

A novel nonlinear optical chromophore with rigid 3-bromo-thiophene (denoted as BTC) as a site-isolation group to suppress the dipole-dipole interaction, was designed and synthesized. UV–vis absorption indicated that BTC showed intensified absorption and large bathochromic solvatochromism. The electro-optic performance studies displayed a highest r 33 value (93 pm/V) at high chromophore loading density of 45%, which indicated that the dipole-dipole interactions were effectively suppressed. The Crystal analysis further demonstrated that the face-to-face antiparallel packing with a long distance of 7.388 Ǻ between the neighboring chromophores was observed. This weak packing interactions suggested that BTC chromophores can be well isolated in electro-optic materials for chromophores’ high efficient alignment. The excellent electro-optic performances endowed BTC potential application in the high-performance electro-optic materials. [ABSTRACT FROM AUTHOR]

Abstract: A series of novel second-order nonlinear optical chromophores containing additional heteroatoms in donor moieties has been synthesized and systematically characterized. The resulting nonlinear optical chromophores exhibited both good thermal stability (the decomposition temperature in the range of 249 °C–275 °C) and good solubility in common organic solvents such as chloroform, acetone and N, N-dimethyl formamide. In order to investigate the influence of additional heteroatom on the electro-optic activities, UV–Vis spectra and density functional theory calculations were carried out. The results revealed that the donor derived from m-phenylenediamine had higher electron density compared with other three donors. As to electro-optic activities, the doped polymer film-C displayed the highest electro-optic coefficient value of 31 pm/v at the doping concentration of 20 wt%. All these results indicated that the nonlinear optical activities could be enhanced by introducing suitable additional heteroatoms into donor moiety. [Copyright &y& Elsevier]