Greatly enhanced second-order nonlinear optical susceptibilities in donor-acceptor organic molecules

Katz, Howard E.; Singer, Kenneth D.; Sohn, John E.; Dirk, Carl W.; King, L. A.; Gordon, H. McL.

doi:10.1021/ja00255a079

Cited by 280 publications

(85 citation statements)

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“…Anal. Calcd for [C22H20NO 4 (C 6 Polymer 5. 5 (0.24 g, 1.42 mmol) was diazotizated in acetic acid with 0.10 g (1.45 mmol) of sodium nitrite, then added to a acetone solution of polymer 1 (0.290 g) containing 2 g of anhydrous sodium acetate, stirred for 10 h, treated as described above, yielding 0.546 g of polymer 5.…”

Section: -Aminophenyl 2-hydroxyethyl Sulfone (8)mentioning

confidence: 99%

Synthesis and Characterization of Photonic Polyesters Containing Azo Chromophore in the Side Chain

Qiu

Zhang

Zhai

et al. 1996

Polym J

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ABSTRACT:A series of polyesters with covalently attached push-pull azobenzene groups have been synthesized and characterized. Some important properties for photonic applications such as thermal stability, solubility, and film forming behavior are investigated and discussed.KEY WORDS Polyester / Push-Pull Azobenzene Group / Azo Chromophore / NLO Materials / Photonic / The studies of side chain polymers have received much attention. For photonic applications, side chain polymers have several advantages comparing with guest-host systems or main chain polymers: a high chromophore concentration can be incorporated into a polymer system without crystallization and phase separation; the glass transition temperature ( Tg) of such system is substantially higher than that of a guest-host system containing the same concentration of chromophore molecules; chromophore in the side chain polymer is not restricted severely as in main chain polymer, so electric poling is still reasonably effective.The synthesis of a polyester with DR-I as side chain was reported by Chen and his coworkers. 1 In the present work, we have synthesized a series of polyesters with covalently attached different push-pull azobenzene groups. The chemical structures of the polymers are shown in Scheme 3. Different from the conventional method, these polymers were synthesized by firstly forming colorless polyester and then by further reaction of the colorless polyester and diazonium salts as shown in Schemes 2 and 3. The polymers prepared in our work have chromophore contents of29-74% in weight, much higher than that in guest-host polymers. These polymers are soluble in many organic solvents, and can be made into thin films by spin-coating. We will also report other characterizations of the polymers. EXPERIMENT AL Terephthalaldehyde (1)It was prepared according to a literature procedure. 2 At first, tetrabromo-p-xylene was synthesized by bromination of p-xylene, and then the tetrabromide was hydrolyzed in concentrated sulfuric acid to form 1. mp l 15-l 16°C (literature: l 15-l l6°C). p-Phenylenediacrylic Acid (2)The mixture of I ( 6.0 g, 0.044 mo)), anhydrous sodium acetate (12.0 g, 0.146 mo!) and redistilled acetic anhydride (10.8g, 0.106mol) were reacted at 150°C for 2h, and then another I 0.8 g of acetic anhydride was added. The reaction mixture was heated for 15 h, dissolved in sodium carbonate solution and filtered. To the filtrate was added 120 ml of 2 M hydrochloric acid. The resulting product was washed with water, air-dried and then extracted with hot acetic acid to remove monoacrylic acid. It gave compound 2 in 41 % yield. mp > 360°C. IR Vo-H 3200-2400cm-1 (br), Vc=o 1675cm-1 . MS: 218 (M+), 173 (M+ -COOH), 128 (M+ -2COOH). (3) 2 (6.0 g, 0.028 mo)) and anhydrous potassium carbonate (12.0 g, 0.086 mo!) were refluxed in 40 ml of redistilled thionyl chloride for 16 h. Excess thionyl chloride was removed by distillation. The residue was extracted with hot petroleum ether, and allowed to cool. The precipitated crystals were recrystallized from petrole...

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Section: -Aminophenyl 2-hydroxyethyl Sulfone (8)mentioning

confidence: 99%

Synthesis and Characterization of Photonic Polyesters Containing Azo Chromophore in the Side Chain

Qiu

Zhang

Zhai

et al. 1996

Polym J

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“…Thus, we decided to calculate the exciton binding energy (E b ), in order to understand better the transport characteristics of modified sumanene. A special interest in the study of organic materials lies in the fact that nonlinear optical (NLO) response is basically microscopic in origin, thus provides the possibility of using theoretical modeling together with synthetic flexibility to design and produce novel materials [13][14][15]. Due to their large optical susceptibilities, inherent ultrafast response times and high optical thresholds for laser power, organic nonlinear optical materials have a great deal of attention.…”

Section: Introductionmentioning

confidence: 99%

Aromaticity, response, and nonlinear optical properties of sumanene modified with boron and nitrogen atoms

2014

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We investigated the effects of substitution on the sumanene benzylic CH2 groups with BH and NH groups using density functional theory computations. Our study shows that various properties of sumanene could be finely tuned for the application in the areas closely related to the materials science. Structural properties are significantly altered with such modifications and other properties as well. Charge distributions were evaluated through natural population analysis (NPA), while stability of investigated structures was investigated using quantum molecular descriptors. Using molecular orbital analysis further insight into the effects of substitution was obtained. Potential of sumanene as a candidate for application in the field of organic electronics is assessed through calculations of exciton binding energy. Non-linear optical properties of investigated structures were investigated using the first hyperpolarizability tensor. Special attention was paid to the aromaticity of sumanene. This property was evaluated employing NICS parameter while for detailed study of obtained results we used NBO and NBOdel analysis.

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“…The aromatic/quinoidal ring is critical in maintaining a charge-separated state; the stability associated with an aromatic moiety playing an important part in determining the geometry of the molecule. The extent to which this effect influences the non-linearity and polarity can be seen by comparing 1 to adducts of TCNE (tetracyanoethylene) 34 which are molecules containing the tricyanovinyl acceptor group. These molecules are predominantly non charge separated and reside on the left hand side (LHS) of the BLA diagrams.…”

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confidence: 99%

Highly Dipolar, Optically Nonlinear Adducts of Tetracyano-p-quinodimethane: Synthesis, Physical Characterization, and Theoretical Aspects

et al. 1997

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A new series of nonlinear optical molecules are described where the ground state polarization is predominantly zwitterionic when the molecules are dissolved in solution. The molecules, which are derived in general from facile reactions between tertiary amines and tetracyano-p-quinodimethane (TCNQ), are of a type where the stabilization of the charge-separated ground state is favored by an increase in aromaticity over the neutral, quinoidal forms of the molecules. The measured second-order optical nonlinearity of one in the series has been measured by hyper-Rayleigh scattering and a figure of merit value, µβ(0), being the product of the dipole moment and static first hyperpolarizability, is found to be 9500 × 10 -48 esu. This value, which is higher than most other reported values, is taken from studies in chlorinated solvents of relatively low polarity, but the discussion emphasizes the evolution of µβ(0) with solvent polarity, showing that even higher values could be expected with only modest increases in the polarity of the surrounding medium. The analysis of experimental data taken during dipole moment studies is thoroughly examined, and it is concluded that full account must be taken of the molecular shape to correlate the results with theoretical calculations. An ellipsoidal reaction field model is preferred for these highly one-dimensional molecules having strongly anisotropic polarizabilities.

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Greatly enhanced second-order nonlinear optical susceptibilities in donor-acceptor organic molecules

Cited by 280 publications

References 0 publications

Synthesis and Characterization of Photonic Polyesters Containing Azo Chromophore in the Side Chain

Synthesis and Characterization of Photonic Polyesters Containing Azo Chromophore in the Side Chain

Aromaticity, response, and nonlinear optical properties of sumanene modified with boron and nitrogen atoms

Highly Dipolar, Optically Nonlinear Adducts of Tetracyano-p-quinodimethane: Synthesis, Physical Characterization, and Theoretical Aspects

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