Synthesis and non‐linear optical characteristics of crosslinked and linear epoxy polymers with pendant tolane chromophores

Zentel, Rudolf; Jungbauer, D.; Twieg, Robert J.; Yoon, Do Young; Willson, C. Grant

doi:10.1002/macp.1993.021940310

Cited by 20 publications

(6 citation statements)

References 14 publications

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“…26 This nitration yielded 1-iodo-3,4-dinitrobenzene ( 1 ), which was then reduced using Sn over HCl to yield 1-iodobenzene-3,4-diamine ( 2 ). 27 Then, the diamine was reacted with 2,5-dihydroxy-1,4-benzoquinone in ethanol to produce 7-iodo-2,3-bis(hydroxyl)phenazine ( 3 ), which was further alkylated without purification. 7-Iodo-2,3-bis(octyloxy)phenazine ( 4 ) was then used in a Sonogashira coupling reaction with triisopropylsilyl (TIPS) acetylene to yield 7-triisopropylsilylethynyl-2,3-bis(octyloxy)phenazine ( 5 ).…”

Section: Results and Discussionmentioning

confidence: 99%

Understanding the Electronic Properties of Acceptor–Acceptor′–Acceptor Triads

et al. 2019

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In order to develop new organic materials for optoelectronic applications, a fundamental understanding of the electronic properties of specific chromophore combinations must be realized. To that end, we report “model” acceptor (A)–acceptor′ (A′)–acceptor (A) triads in which the pendants (A′) we selected are well-known components of organic optoelectronic applications. Our pendants are sandwiched between two dialkoxyphenazine (A) through an alkyne bond. The A′ was systematically increased in electron-deficiency from benzothiadiazole ( BTD-P ) to naphthalene diimide with octyl ( NDI-O-P ) or ethylhexyl groups ( NDI-EH-P ) to perylene diimide with ethylhexyl ( PTCDI-EH-P ) to assess changes in the electronic properties of the resultant molecules. Characterizations were performed using both experimental and theoretical methods. From optical and cyclic voltammetry, we found that the electron deficiency of each pendant was directly correlated to the energy level of the lowest unoccupied molecular orbital ( E LUMO ). When examining the simple molecular orbital diagrams produced at the B3LYP/6-31G* level of theory, the LUMOs were, as expected, primarily localized on the more electron-deficient pendants. In terms of the energy level of the highest occupied molecular orbital ( E HOMO ), the numerical values obtained experimentally also correlated with values obtained computationally. Attempting to construct a simplified model that would explain these correlated values was not as readily apparent, given the disparate physical characteristics of these compounds. For example, BTD-P and NDI-O-P/NDI-EH-P achieved planarity when computationally optimized, but PTCDI-EH-P adapted a “buckled” geometry on the central PTCDI, consequently forcing the attached phenazines out-of-plane. The title compounds showed solvent polarity-dependent fluorescence, which is indicative of intramolecular charge transfer. In conjunction with our theoretical study, the current system can be viewed as an extension of donor–acceptor–donor systems. Thermal properties characterized by differential scanning calorimetry revealed that reversible phase transitions were only observed for BTD-P . In addition, BTD-P was found to be an efficient gelator in 1,1,1-trichloroethane and toluene. The other compounds in this study did not form gels in any of the solvents tested, which may have been a result of the alkyl groups on the pendants hampering the fibrillation process.

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Section: Results and Discussionmentioning

confidence: 99%

Understanding the Electronic Properties of Acceptor–Acceptor′–Acceptor Triads

et al. 2019

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“…To suppress this reorientation, rigid polymer backbones exhibiting high T g 's were synthesized. This can be achieved either in cross‐linked systems2–11 or with thermoplastics like polyimides12–17 or maleimide‐based polymers 18–28…”

Section: Introductionmentioning

confidence: 99%

Chromophore‐Functionalized Poly(ether sulfone)s with High Poling Stabilities of the Nonlinear Optical Effect

Ballet

Picard

Verbiest

et al. 2003

Macro Chemistry & Physics

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Summary: Nonlinear optical (NLO) polymers with high glass transition temperatures were prepared by the functionalization of poly(ether sulfone)s with hydroxyalkyl chromophores via the Mitsunobu reaction. Glass transition temperatures obtained were in the range of 158–212 °C. Thin spin‐coated films of the polymers were corona‐poled and analyzed by second‐harmonic generation measurements; second‐order susceptibility values (d33) up to 181 pm · V−1 were obtained. Poled‐order stability measurements over a period of 1 600 h showed that the percentage of the remaining NLO‐response at 125 °C was 84–96% under nitrogen and 54–76% in air.

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“…It has often been observed that poled NLO polymer materials undergo temporal relaxation of the dipolar orientation, which so far has prevented their use in practical EO devices. During the past decade, research has focused on improving the temporal stability of the polar order via the synthesis of high‐glass‐transition‐temperature ( T g ) polymers or the creation of thermocrosslinked or photocrosslinked polymer networks after poling,3–13 both exhibiting high thermal stability for the EO coefficients. However, their processing is usually rather difficult.…”

Section: Introductionmentioning

confidence: 99%

Crosslinkable maleimide copolymers for stable NLO properties

Serhatlı

Yaǧcı

Hattemer

et al. 2001

J. Polym. Sci. A Polym. Chem.

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Second-order, nonlinear optical polymers based on epoxy-substituted methylvinylisocyanates and N-substituted maleimides were synthesized and characterized with spectral and thermal analysis. The photocrosslinking and thermal-crosslinking reactions of copolymers with different chromophore contents were studied. Thermally induced crosslinking during the poling process, performed at the glass-transition temperature (T g ), was prevented by T g being decreased through the addition of a plasticizer. Electrooptic coefficients (r 33 ), measured for crosslinked and noncrosslinked systems, had similar absolute values and relaxation dynamics. This behavior was explained in terms of the similar rotational mobility of the chromophore units and the paucity of crosslinking sites.

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Synthesis and non‐linear optical characteristics of crosslinked and linear epoxy polymers with pendant tolane chromophores

Cited by 20 publications

References 14 publications

Understanding the Electronic Properties of Acceptor–Acceptor′–Acceptor Triads

Understanding the Electronic Properties of Acceptor–Acceptor′–Acceptor Triads

Chromophore‐Functionalized Poly(ether sulfone)s with High Poling Stabilities of the Nonlinear Optical Effect

Crosslinkable maleimide copolymers for stable NLO properties

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