A soluble low bandgap poly （pyrrole methine） with alkoxyl substituent, poly {（3-hexanoyl）pyrrole-[2,5- diyl（p-tetradecyloxybenzylidene）]} （PHPDTBE）, was synthesized and characterized by 1H nuclear magnetic res...A soluble low bandgap poly （pyrrole methine） with alkoxyl substituent, poly {（3-hexanoyl）pyrrole-[2,5- diyl（p-tetradecyloxybenzylidene）]} （PHPDTBE）, was synthesized and characterized by 1H nuclear magnetic resonance （1H-NMR）, Fourier transform-infrared （FT-IR）, elemental analysis （EA） and gel permeation chromatography （GPC）. PHPDTBE was readily soluble in weak polar organic solvents. The absorption peaks of PHPDTBE solution and film were located at around 458 and 484 nm, respectively. The optical bandgaps of PHPDTBE film for indirect allowed and direct allowed transitions were measured to be 1.66 and 2.35 eV, respectively. PHPDTBE film had few defects in the energy band and the Urbach energy of PHPDTBE film was calculated to be about 0.19 eV. The resonant third-order nonlinear optical susceptibilities of PHPDTBE solution and film measured by degenerate four-wave mixing （DFWM） technique at 532nm were all in the order of 10 8 esu, which was about 1-3 orders of magnitude larger than that of the other ordinary n-conjugation polymers.展开更多
Third-order nonlinear optical (NLO) materials have broad application prospects in high-density data storage, optical computer, modern laser technology, and other high-tech industries. The structures and frequencies of...Third-order nonlinear optical (NLO) materials have broad application prospects in high-density data storage, optical computer, modern laser technology, and other high-tech industries. The structures and frequencies of Dinaphtho[2,3-b:2’,3’-d]thiophene-5,7,12,13-tetraone (DNTTRA) and its 36 derivatives containing azobenzene were calculated by using density functional theory B3LYP and M06-2X methods at 6-311++g(d, p) level, respectively. Besides, the atomic charges of natural bond orbitals (NBO) were analyzed. The frontier orbitals and electron absorption spectra of A-G5 molecule were calculated by TD-DFT (TD-B3LYP/6-311++g(d, p) and TD-M06-2X/6-311++g(d, p)). The NLO properties were calculated by effective finite field FF method and self-compiled program. The results show that 36 molecules of these six series are D-π-A-π-D structures. The third-order NLO coefficients γ (second-order hyperpolarizability) of the D series molecules are the largest among the six series, reaching 10<sup>7</sup> atomic units (10<sup><span style="color:#4F4F4F;font-family:-apple-system, " font-size:14px;white-space:normal;background-color:#ffffff;"="">-</span>33</sup> esu) of order of magnitude, showing good third-order NLO properties. Last, the third-order NLO properties of the azobenzene ring can be improved by introducing strong electron donor groups (e.g. -N(CH<sub>3</sub>)<sub>2</sub> or -NHCH<sub>3</sub>) in the azobenzene ring, so that the third-order NLO materials with good performance can be obtained.展开更多
合成1种查尔酮衍生物1-（芘-1-基）-3-（苯并噻吩-3-基）丙烯酮（PBTAK）,经IR,1 H NMR,13C NMR和HR-MS对其结构进行表征.采用4f相位相干成像技术测定了它的三阶非线性光学性质并确定了相关参数：脉宽为4nm,激光波长为460nm,非线性吸收...合成1种查尔酮衍生物1-（芘-1-基）-3-（苯并噻吩-3-基）丙烯酮（PBTAK）,经IR,1 H NMR,13C NMR和HR-MS对其结构进行表征.采用4f相位相干成像技术测定了它的三阶非线性光学性质并确定了相关参数：脉宽为4nm,激光波长为460nm,非线性吸收系数β=0.23×10-9 m/W,非线性折射率n2=-0.50×10-16 m2/W,三阶非线性极化率χ（3）=9.37×10-21 C;同时测定了紫外光谱、荧光光谱和DSC曲线.运用密度泛函方法计算了PBTAK的分子轨道能量和极化率,结果表明电子转移能在分子内部进行,显示出良好的非线性光学活性.展开更多
A novel soluble π-conjugated polymer, poly[(3-octanoylpyrrole-2,5-diyl)-p-nitrobenzylidene] (POPNBE), was synthesized by a five-step reaction. As a result of introducing a long acyl to pyrrole at 3-position, the poly...A novel soluble π-conjugated polymer, poly[(3-octanoylpyrrole-2,5-diyl)-p-nitrobenzylidene] (POPNBE), was synthesized by a five-step reaction. As a result of introducing a long acyl to pyrrole at 3-position, the polymer can be easily solved in polar solvents and be processed into films. The chemical structures of the intermediates and POPNBE were characterized by FTIR, 1H NMR, and UV-Vis-NIR spectrometries. The absorption band in the range of 400-600 nm in the UV-Vis-NIR spectrum is due to the π-π * band gap transition. The optical band gap of POPNBE obtained from the optical absorption is about 1.72 eV. The resonant third-order nonlinear optical property of POPNBE at 532 nm was studied by using the degenerate four-wave mixing(DFWM) technique. The resonant third-order nonlinear optical susceptibility of POPNBE is about 3.42×10 -8 esu.展开更多
A novel biferocene trinuclear complex for Schiff base ligand S-methyl-N- (ferrocenyl-1-methyl -methylidene) dithiocarbazate thereafter abbreviated as HL) is described. X-ray diffraction studies established the structu...A novel biferocene trinuclear complex for Schiff base ligand S-methyl-N- (ferrocenyl-1-methyl -methylidene) dithiocarbazate thereafter abbreviated as HL) is described. X-ray diffraction studies established the structure of the palladium complex, PdL2. The geometry of Pd (II) in the complex is close to square planar and in novel cis-configuration with two ferrocene moieties on the same side. Degenerate four-wave mixing (DFWM) measurements show that the complex exhibit obvious nonlinear optical response.展开更多
A novel Schiff base ligand (HL) derived from S-methyldithiocabazate and pmethoxylbenzaldehyde was prepared and characterized. The Schiff base ligand acts as a single negatively charged bidentate ligand fondng D-M-D ty...A novel Schiff base ligand (HL) derived from S-methyldithiocabazate and pmethoxylbenzaldehyde was prepared and characterized. The Schiff base ligand acts as a single negatively charged bidentate ligand fondng D-M-D type comPlex (D=donor, M=metal). Single crystal X-ray diffraction analysis of the copper(Ⅱ) complex established that the geometry around Cu (Ⅱ) is square-planar with two equivalent M-N and M-S bonds. The two phenyl rings and the coordinated plane are almost in one plane fotheng an electronic delocalization system. Their thirdorder response was also studied.展开更多
The syntheses and characterization of novel biferrocene trinuclear complexes of Schiff base ligand, S methyl N (ferrocenyl 1 methyl methylidene)dithiocarbazate [hereafter abbreviated as HL (1)], are described. The X r...The syntheses and characterization of novel biferrocene trinuclear complexes of Schiff base ligand, S methyl N (ferrocenyl 1 methyl methylidene)dithiocarbazate [hereafter abbreviated as HL (1)], are described. The X ray diffraction studies have established the structures of PdL 2 (3) and CuL 2 (4). The geometry of Pd(Ⅱ) in (3) is close to a square plane and in the novel cis configuration the two ferrocene moieties are in cis configuration, while that of Cu(Ⅱ) in (4) is close to a tetrahedral configuration. The electrochemical measurements suggested that the square planar configuration of Ni(Ⅱ) and Pd(Ⅱ) moieties can effectively transmit the redox effects of the ferrocene moieties, while the tetrahedral configuration of the Cu(Ⅱ) complex can not transmit the redox effects. The degenerate four wave mixing (DFWM) measurements showed that the complexes exhibit obviously nonlinear optical (NLO) response. The magnitude of their third order NLO susceptibility can be explained by their structure and electrochemical properties.展开更多
文摘A soluble low bandgap poly （pyrrole methine） with alkoxyl substituent, poly {（3-hexanoyl）pyrrole-[2,5- diyl（p-tetradecyloxybenzylidene）]} （PHPDTBE）, was synthesized and characterized by 1H nuclear magnetic resonance （1H-NMR）, Fourier transform-infrared （FT-IR）, elemental analysis （EA） and gel permeation chromatography （GPC）. PHPDTBE was readily soluble in weak polar organic solvents. The absorption peaks of PHPDTBE solution and film were located at around 458 and 484 nm, respectively. The optical bandgaps of PHPDTBE film for indirect allowed and direct allowed transitions were measured to be 1.66 and 2.35 eV, respectively. PHPDTBE film had few defects in the energy band and the Urbach energy of PHPDTBE film was calculated to be about 0.19 eV. The resonant third-order nonlinear optical susceptibilities of PHPDTBE solution and film measured by degenerate four-wave mixing （DFWM） technique at 532nm were all in the order of 10 8 esu, which was about 1-3 orders of magnitude larger than that of the other ordinary n-conjugation polymers.
文摘Third-order nonlinear optical (NLO) materials have broad application prospects in high-density data storage, optical computer, modern laser technology, and other high-tech industries. The structures and frequencies of Dinaphtho[2,3-b:2’,3’-d]thiophene-5,7,12,13-tetraone (DNTTRA) and its 36 derivatives containing azobenzene were calculated by using density functional theory B3LYP and M06-2X methods at 6-311++g(d, p) level, respectively. Besides, the atomic charges of natural bond orbitals (NBO) were analyzed. The frontier orbitals and electron absorption spectra of A-G5 molecule were calculated by TD-DFT (TD-B3LYP/6-311++g(d, p) and TD-M06-2X/6-311++g(d, p)). The NLO properties were calculated by effective finite field FF method and self-compiled program. The results show that 36 molecules of these six series are D-π-A-π-D structures. The third-order NLO coefficients γ (second-order hyperpolarizability) of the D series molecules are the largest among the six series, reaching 10<sup>7</sup> atomic units (10<sup><span style="color:#4F4F4F;font-family:-apple-system, " font-size:14px;white-space:normal;background-color:#ffffff;"="">-</span>33</sup> esu) of order of magnitude, showing good third-order NLO properties. Last, the third-order NLO properties of the azobenzene ring can be improved by introducing strong electron donor groups (e.g. -N(CH<sub>3</sub>)<sub>2</sub> or -NHCH<sub>3</sub>) in the azobenzene ring, so that the third-order NLO materials with good performance can be obtained.
文摘A novel soluble π-conjugated polymer, poly[(3-octanoylpyrrole-2,5-diyl)-p-nitrobenzylidene] (POPNBE), was synthesized by a five-step reaction. As a result of introducing a long acyl to pyrrole at 3-position, the polymer can be easily solved in polar solvents and be processed into films. The chemical structures of the intermediates and POPNBE were characterized by FTIR, 1H NMR, and UV-Vis-NIR spectrometries. The absorption band in the range of 400-600 nm in the UV-Vis-NIR spectrum is due to the π-π * band gap transition. The optical band gap of POPNBE obtained from the optical absorption is about 1.72 eV. The resonant third-order nonlinear optical property of POPNBE at 532 nm was studied by using the degenerate four-wave mixing(DFWM) technique. The resonant third-order nonlinear optical susceptibility of POPNBE is about 3.42×10 -8 esu.
文摘A novel biferocene trinuclear complex for Schiff base ligand S-methyl-N- (ferrocenyl-1-methyl -methylidene) dithiocarbazate thereafter abbreviated as HL) is described. X-ray diffraction studies established the structure of the palladium complex, PdL2. The geometry of Pd (II) in the complex is close to square planar and in novel cis-configuration with two ferrocene moieties on the same side. Degenerate four-wave mixing (DFWM) measurements show that the complex exhibit obvious nonlinear optical response.
文摘A novel Schiff base ligand (HL) derived from S-methyldithiocabazate and pmethoxylbenzaldehyde was prepared and characterized. The Schiff base ligand acts as a single negatively charged bidentate ligand fondng D-M-D type comPlex (D=donor, M=metal). Single crystal X-ray diffraction analysis of the copper(Ⅱ) complex established that the geometry around Cu (Ⅱ) is square-planar with two equivalent M-N and M-S bonds. The two phenyl rings and the coordinated plane are almost in one plane fotheng an electronic delocalization system. Their thirdorder response was also studied.
文摘The syntheses and characterization of novel biferrocene trinuclear complexes of Schiff base ligand, S methyl N (ferrocenyl 1 methyl methylidene)dithiocarbazate [hereafter abbreviated as HL (1)], are described. The X ray diffraction studies have established the structures of PdL 2 (3) and CuL 2 (4). The geometry of Pd(Ⅱ) in (3) is close to a square plane and in the novel cis configuration the two ferrocene moieties are in cis configuration, while that of Cu(Ⅱ) in (4) is close to a tetrahedral configuration. The electrochemical measurements suggested that the square planar configuration of Ni(Ⅱ) and Pd(Ⅱ) moieties can effectively transmit the redox effects of the ferrocene moieties, while the tetrahedral configuration of the Cu(Ⅱ) complex can not transmit the redox effects. The degenerate four wave mixing (DFWM) measurements showed that the complexes exhibit obviously nonlinear optical (NLO) response. The magnitude of their third order NLO susceptibility can be explained by their structure and electrochemical properties.
