Synthesis and characterization of photorefractive polymers with triphenylamine unit and NLO chromophore unit on a side chain

Abstract

Acrylate-type copolymers (TPA-DCV) consisting of triphenylamine (TPA) unit as a hole transport agent and dicyanovinyl aniline (DCV) as a second-order nonlinear optical (NLO) chromophore on a side chain were synthesized. The polymers showed good solubility and sufficient morphological stability after film formation. The diffraction efficiency and gain coefficient increased as glass transition temperature decreased TPA-DCV composite doped with fullerene (C 60 ) and dibutyl phthalate had a high photoconductivity of 5.1 Â 10 À12 S/cm at the applied electric field of 50 V/ "m. Diffraction efficiency and response rate were measured as functions of the parameters determining the photoconductivity (e.g. applied electric field, the density of the photocharges generated and writing beam intensity). The maximum diffraction efficiency and gain coefficient were 12.9% and 64 cm À1 , respectively, at an applied electric field of 80 V/"m. The maximum response time of 700 msec was obtained at the applied electric field of 80 V/"m. Photoconductivity, response rate and diffraction efficiency increased with the increase of the applied electric field. Field dependence of the response rate is attributed to the charge generation efficiency and/ or the drift mobility. A similar power dependence of the photoconductivity and the response rate on the writing beam intensity was observed. The response rate and diffraction efficiency showed a good linear relationship with the logarithm of the photoconductivity.Photorefractive Polymers / 355 FIGURE 7. Photoconductivity dependencies of (a) the response rate and (b) diffraction ef®ciency:

Synthesis and Solution Aggregation Studies of a Suite of Mixed Neutral and Zwitterionic Chromophores for Second-Order Nonlinear Optics

“…The solvent was removed in vacuo, and the crude product was recrystallized from ethanol to give 25b (2.9 g, 63%) as a pale brown solid. Spectral properties are in agreement with the literature: , mp 98–100 °C; λ max (CHCl 3 ) 432 log 10 ε 4.72, (1,4-dioxane) 423 log 10 ε 4.69, (DMF) 441 log 10 ε 4.71, (MeOH) 430 log 10 ε 4.70, (THF) 431 log 10 ε 4.71; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.83 (2 H, d, J = 9.1 Hz, Ar H ), 7.46 (1 H, s, C H C(CN) 2 ), 6.80 (2 H, d, J = 9.2 Hz, Ar H ), 3.92 (2 H, t, J = 5.6 Hz, NC H 2 CH 2 OH), 3.69 (2 H, t, J = 5.6 Hz, NCH 2 C H 2 OH), 3.21 (3 H, s, C H 3 ).…”

“…The solvent was removed in vacuo, and the crude product was recrystallized from ethanol to give 25b (2.9 g, 63%) as a pale brown solid. Spectral properties are in agreement with the literature: 51,52 To a solution of 25a (1.0 g, 2.6 mmol) and succinic anhydride (0.51 g, 5.1 mmol) in anhydrous dichloromethane (30 mL), 4-dimethylaminopyridine (0.31 g, 2.6 mmol) and pyridine (0.65 mL, 8.0 mmol) were added under N 2 . The reaction mixture was stirred at room temperature overnight and then washed with brine (30 mL) and water (30 mL).…”

Synthesis and Solution Aggregation Studies of a Suite of Mixed Neutral and Zwitterionic Chromophores for Second-Order Nonlinear Optics

“…The solvent was removed in vacuo, and the crude product was recrystallized from ethanol to give 25b (2.9 g, 63%) as a pale brown solid. Spectral properties are in agreement with the literature: , mp 98–100 °C; λ max (CHCl 3 ) 432 log 10 ε 4.72, (1,4-dioxane) 423 log 10 ε 4.69, (DMF) 441 log 10 ε 4.71, (MeOH) 430 log 10 ε 4.70, (THF) 431 log 10 ε 4.71; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.83 (2 H, d, J = 9.1 Hz, Ar H ), 7.46 (1 H, s, C H C(CN) 2 ), 6.80 (2 H, d, J = 9.2 Hz, Ar H ), 3.92 (2 H, t, J = 5.6 Hz, NC H 2 CH 2 OH), 3.69 (2 H, t, J = 5.6 Hz, NCH 2 C H 2 OH), 3.21 (3 H, s, C H 3 ).…”

“…The solvent was removed in vacuo, and the crude product was recrystallized from ethanol to give 25b (2.9 g, 63%) as a pale brown solid. Spectral properties are in agreement with the literature: 51,52 To a solution of 25a (1.0 g, 2.6 mmol) and succinic anhydride (0.51 g, 5.1 mmol) in anhydrous dichloromethane (30 mL), 4-dimethylaminopyridine (0.31 g, 2.6 mmol) and pyridine (0.65 mL, 8.0 mmol) were added under N 2 . The reaction mixture was stirred at room temperature overnight and then washed with brine (30 mL) and water (30 mL).…”

Triphenylamine-Cored Bifunctional Organic Molecules for Two-Photon Absorption and Photorefraction

“…Photorefractivity. It is expected that both STEH and SSEH series could exhibit photorefractivity due to the presence of photoconducting triphenylamine core and conjugated push−pull structures in the arms. Because the STEH series was easily fabricated to excellent optical films suitable for photorefractive measurement, we have limited our attention on STEH series in this work.…”

Photoluminescence and excimer emission of functional groups in light‐emitting polymers

“…The acryloyl derivative of triphenylamine 4 was prepared by the reduction of 4‐( N , N ‐diphenylamino)benzaldehyde to 4‐( N , N ‐diphenylamino)benzyl alcohol with sodium borohydride and subsequent esterification with acryloyl chloride, summarized in Scheme . The polymer of 4 was used for hole transport 13–15. The methacryloyloxyethylureido derivative of triphenylamine 5 was obtained by the reduction of 4‐nitrophenyldiphenylamine by hydrogenation to 4‐diphenylaminoaniline and reacting it with IEM, similar to the synthetic procedure used in ref.…”

Synthesis and Solution Aggregation Studies of a Suite of Mixed Neutral and Zwitterionic Chromophores for Second-Order Nonlinear Optics

“…The solvent was removed in vacuo, and the crude product was recrystallized from ethanol to give 25b (2.9 g, 63%) as a pale brown solid. Spectral properties are in agreement with the literature: , mp 98–100 °C; λ max (CHCl 3 ) 432 log 10 ε 4.72, (1,4-dioxane) 423 log 10 ε 4.69, (DMF) 441 log 10 ε 4.71, (MeOH) 430 log 10 ε 4.70, (THF) 431 log 10 ε 4.71; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.83 (2 H, d, J = 9.1 Hz, Ar H ), 7.46 (1 H, s, C H C(CN) 2 ), 6.80 (2 H, d, J = 9.2 Hz, Ar H ), 3.92 (2 H, t, J = 5.6 Hz, NC H 2 CH 2 OH), 3.69 (2 H, t, J = 5.6 Hz, NCH 2 C H 2 OH), 3.21 (3 H, s, C H 3 ).…”

“…The solvent was removed in vacuo, and the crude product was recrystallized from ethanol to give 25b (2.9 g, 63%) as a pale brown solid. Spectral properties are in agreement with the literature: 51,52 To a solution of 25a (1.0 g, 2.6 mmol) and succinic anhydride (0.51 g, 5.1 mmol) in anhydrous dichloromethane (30 mL), 4-dimethylaminopyridine (0.31 g, 2.6 mmol) and pyridine (0.65 mL, 8.0 mmol) were added under N 2 . The reaction mixture was stirred at room temperature overnight and then washed with brine (30 mL) and water (30 mL).…”

Triphenylamine-Cored Bifunctional Organic Molecules for Two-Photon Absorption and Photorefraction

“…Photorefractivity. It is expected that both STEH and SSEH series could exhibit photorefractivity due to the presence of photoconducting triphenylamine core and conjugated push−pull structures in the arms. Because the STEH series was easily fabricated to excellent optical films suitable for photorefractive measurement, we have limited our attention on STEH series in this work.…”

Photoluminescence and excimer emission of functional groups in light‐emitting polymers

“…The acryloyl derivative of triphenylamine 4 was prepared by the reduction of 4‐( N , N ‐diphenylamino)benzaldehyde to 4‐( N , N ‐diphenylamino)benzyl alcohol with sodium borohydride and subsequent esterification with acryloyl chloride, summarized in Scheme . The polymer of 4 was used for hole transport 13–15. The methacryloyloxyethylureido derivative of triphenylamine 5 was obtained by the reduction of 4‐nitrophenyldiphenylamine by hydrogenation to 4‐diphenylaminoaniline and reacting it with IEM, similar to the synthetic procedure used in ref.…”

Synthesis and Solution Aggregation Studies of a Suite of Mixed Neutral and Zwitterionic Chromophores for Second-Order Nonlinear Optics

“…The solvent was removed in vacuo, and the crude product was recrystallized from ethanol to give 25b (2.9 g, 63%) as a pale brown solid. Spectral properties are in agreement with the literature: , mp 98–100 °C; λ max (CHCl 3 ) 432 log 10 ε 4.72, (1,4-dioxane) 423 log 10 ε 4.69, (DMF) 441 log 10 ε 4.71, (MeOH) 430 log 10 ε 4.70, (THF) 431 log 10 ε 4.71; 1 H NMR (500 MHz, CDCl 3 ) δ: 7.83 (2 H, d, J = 9.1 Hz, Ar H ), 7.46 (1 H, s, C H C(CN) 2 ), 6.80 (2 H, d, J = 9.2 Hz, Ar H ), 3.92 (2 H, t, J = 5.6 Hz, NC H 2 CH 2 OH), 3.69 (2 H, t, J = 5.6 Hz, NCH 2 C H 2 OH), 3.21 (3 H, s, C H 3 ).…”

“…The solvent was removed in vacuo, and the crude product was recrystallized from ethanol to give 25b (2.9 g, 63%) as a pale brown solid. Spectral properties are in agreement with the literature: 51,52 To a solution of 25a (1.0 g, 2.6 mmol) and succinic anhydride (0.51 g, 5.1 mmol) in anhydrous dichloromethane (30 mL), 4-dimethylaminopyridine (0.31 g, 2.6 mmol) and pyridine (0.65 mL, 8.0 mmol) were added under N 2 . The reaction mixture was stirred at room temperature overnight and then washed with brine (30 mL) and water (30 mL).…”

Triphenylamine-Cored Bifunctional Organic Molecules for Two-Photon Absorption and Photorefraction

“…Photorefractivity. It is expected that both STEH and SSEH series could exhibit photorefractivity due to the presence of photoconducting triphenylamine core and conjugated push−pull structures in the arms. Because the STEH series was easily fabricated to excellent optical films suitable for photorefractive measurement, we have limited our attention on STEH series in this work.…”

Photoluminescence and excimer emission of functional groups in light‐emitting polymers

“…The acryloyl derivative of triphenylamine 4 was prepared by the reduction of 4‐( N , N ‐diphenylamino)benzaldehyde to 4‐( N , N ‐diphenylamino)benzyl alcohol with sodium borohydride and subsequent esterification with acryloyl chloride, summarized in Scheme . The polymer of 4 was used for hole transport 13–15. The methacryloyloxyethylureido derivative of triphenylamine 5 was obtained by the reduction of 4‐nitrophenyldiphenylamine by hydrogenation to 4‐diphenylaminoaniline and reacting it with IEM, similar to the synthetic procedure used in ref.…”